KR101888697B1 - Resin composition - Google Patents

Abstract

Disclosed is a resin composition capable of forming a plated conductor layer having a small arithmetic mean roughness and a square root mean square roughness of the surface of an insulating layer and a sufficient peel strength while maintaining a glass transition temperature and a thermal expansion coefficient And to provide an image processing apparatus.
As a solution to the above problems, the present invention has been accomplished in a resin composition containing an epoxy resin, a specific alkoxysilane-modified resin, and an inorganic filler.

Description

Resin composition {RESIN COMPOSITION}

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

2. Description of the Related Art In recent years, miniaturization and high performance of electronic devices have progressed, and in a multilayer printed wiring board, buildup layers have been layered, and wiring has been required to be finer and higher in density.

There have been various studies on this. For example, Patent Document 1 discloses a resin composition comprising an alkoxysilane-modified resin. It is described that an insulating material formed from these compositions can have heat resistance, low thermal expansion, and flame retardancy. However, the performance was not necessarily satisfactory.

Patent Document 1: JP-A-2001-261776

A problem to be solved by the present invention is to provide a process for producing a plating film having a small arithmetic mean roughness and a square root mean square roughness of the surface of an insulating layer and a sufficient peel strength in a wet roughening process while maintaining a glass transition temperature and a thermal expansion rate, And to provide a resin composition capable of forming a conductor layer.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have completed the present invention on a resin composition comprising an epoxy resin, a specific alkoxysilane-modified resin and an inorganic filler.

That is, the present invention includes the following contents.

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

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

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

[4] The resin composition according to any one of [1] to [3], wherein the inorganic filler (C) is 100 parts by mass and the trifunctional alkoxysilane-modified resin (B) .

[5] The thermosetting resin composition according to any one of [1] to [3], wherein the trifunctional alkoxysilane-modified resin (B) is a trifunctional alkoxysilane-modified epoxy resin obtained by modifying a hydroxyl group in a hydroxyl- The resin composition according to any one of the above [1] to [4], which is a phenoxy resin modified with a phenoxy resin.

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

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

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

In formula (1), R ₃ is a linear or branched alkyl group having 1 to 10 carbon atoms or an allyl group, and R ₄ and R ₅ are each independently hydrogen or a straight or branched alkyl group having 1 to 10 carbon atoms. In the formula (1), m represents 1 to 10. In the formula (1), X is selected from a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a bisphenol S type epoxy resin and a novolak phenol resin.

[8] A method for producing a resin composition, which comprises curing a resin composition to form an insulating layer, roughening the surface of the insulating layer, and peeling strength between the conductor layer obtained by plating and the insulating layer is 0.43 kgf / cm to 1.0 kgf / 1] to [7], wherein the insulating layer is formed by curing the surface of the insulating layer and the surface roughness of the insulating layer is 10 nm to 300 nm and the root mean square roughness is 10 nm to 520 nm. Wherein the resin composition is a resin composition.

[9] An adhesive film in which the resin composition described in any one of [1] to [8] above is layered on a support.

[10] A prepreg impregnated with a resin composition as described in any one of [1] to [8] above in a sheet-like reinforcing base material.

[11] A multilayer printed wiring board in which an insulating layer is formed by a cured product of the resin composition described in any one of [1] to [8].

[12] A semiconductor device using the multilayered printed circuit board according to [11].

The arithmetic mean roughness and the root mean square roughness of the surface of the insulating layer in the wet roughening process are small while maintaining the glass transition temperature and the thermal expansion coefficient by using the resin composition containing the epoxy resin, the specific alkoxysilane- , And further it is possible to provide a resin composition capable of forming a plated conductor layer having sufficient peel strength.

The present invention is a resin composition comprising (A) an epoxy resin, (B) a trifunctional alkoxysilane-modified resin, and (C) an inorganic filler. "Trifunctional alkoxysilane" used in the present invention means "a silane compound in which at least one silicon atom is substituted with an alkyl group and an alkoxy group with an oxy group".

≪ (A) Epoxy resin >

Examples of the epoxy resin used in the present invention include, but not limited to, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, phenol novolak epoxy resin, tert- Naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, biphenyl type epoxy resin, Linear epoxy resins, linear epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexanedimethanol type epoxy resins, trimethylol type epoxy resins and halogenated epoxy resins. These may be used alone or in combination of two or more.

Among them, bisphenol A epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, naphthylene ether epoxy resin, butadiene structure epoxy resin, butadiene structure epoxy resin, and the like are preferable from the viewpoints of heat resistance improvement, insulation reliability improvement, Is preferable. Specific examples of the epoxy resin include bisphenol A epoxy resin (Epikote 828EL, YL980 manufactured by Mitsubishi Chemical Corporation), bisphenol F epoxy resin ("jER806H" and "YL983U" manufactured by Mitsubishi Chemical Corporation) ), Naphthalene type bifunctional epoxy resin ("HP4032", "HP4032D", "HP4032SS", "EXA4032SS" manufactured by DIC Corporation), naphthalene type tetrafunctional epoxy resin (HP4700, ), A naphthol type epoxy resin ("ESN-475V" manufactured by Toto Kasei Corporation), an epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industries Ltd.), an epoxy resin having a biphenyl structure "NC3000H", "NC3000L", "NC3100", "YX4000", "YX4000H", "YX4000HK" and "YL6121" manufactured by Mitsubishi Kagaku Co., Ltd.), anthracene epoxy resin YX8800 "manufactured by Kaku Co., Ltd.), naphthylene ether type epoxy resin (" EXA-7310 "manufactured by DIC Corporation," EXA-7311 " , "EXA-7311L", "EXA7311-G3 '), and the like.

The epoxy resin may be used in combination of two or more, but it preferably contains an epoxy resin having two or more epoxy groups in one molecule. Further, an epoxy resin which is an aromatic epoxy resin having two or more epoxy groups in a molecule and is liquid at a temperature of 20 占 폚, and an aromatic epoxy resin having three or more epoxy groups in one molecule and solid at 20 占 폚 The mode is more preferable. On the other hand, the aromatic epoxy resin 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 in combination as the epoxy resin, the resin composition has appropriate flexibility in the case of using the resin composition in the form of an adhesive film, and the cured product of the resin composition has appropriate breaking strength. The mixing ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 2, more preferably 1: 0.3 to 1.8, and further preferably 1: 0.6 to 1.5 in mass ratio.

From the standpoint of improving the mechanical strength and water resistance of the cured product of the resin composition of the present invention, when the nonvolatile component in the resin composition is 100 mass%, the content of the epoxy resin is preferably 3 to 40 mass% , More preferably from 5 to 35 mass%, still more preferably from 10 to 30 mass%.

≪ (B) Trifunctional alkoxysilane-modified resin >

In the (B) trifunctional alkoxysilane-modified resin to be used in the present invention, the term "trifunctional alkoxysilane" means that the "trifunctional alkoxysilane" is a silane compound having three oxy- It is not limited. Specifically, it is represented by R ₁ -Si- (OR ₂ ) ₃ . Herein, R ₁ represents a lower alkyl (preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably a linear chain having 1 to 6 carbon atoms More preferably a linear or branched alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group, an ethyl group, a propyl group, still more preferably a methyl group) or an allyl group. R ₂ is preferably a hydrogen atom or a lower alkyl (preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably a linear chain having 1 to 6 carbon atoms More preferably a linear or branched alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group, an ethyl group, a propyl group, still more preferably a methyl group), an allyl group or a silyl group. Thus, the trifunctional alkoxysilane-modified resin (B) is not particularly limited, but is preferably a resin obtained by modifying a silane compound in which an oxy group containing an alkyl group and an alkoxy group is substituted with at least one silicon atom. Further, a trifunctional alkoxysilane-modified epoxy resin in which the hydroxyl group in the hydroxyl group-containing epoxy resin is modified with silane or a trifunctional alkoxysilane-modified phenol resin in which the phenolic hydroxyl group in the phenol resin is silane-modified is more preferable.

As the above-mentioned hydroxyl group-containing epoxy resin, various bisphenol-type epoxy resins can be used. The bisphenol type epoxy resin is obtained by reacting a bisphenol with a halo epoxide such as epichlorohydrin or? -Methyl epichlorohydrin. Examples of the bisphenols include phenol or a reaction product of 2,6-dihalophenol with aldehydes or ketones such as formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone and benzophenone, Oxidation by hydroquinone, hydrogenated bisphenol obtained by hydrogenating them, and the like. The bisphenols may be partially substituted with 4,4'-dihydroxybiphenyl, trihydroxydiphenyldimethylethane, long-chain bisphenols, resorcin, salighenin, and the like. Of these bisphenol-type epoxy resins, bisphenol A-type epoxy resins are preferable from the viewpoint of improving compatibility.

As the phenol resin, novolac phenol resins obtained by reacting phenols and aldehydes in the presence of an acid catalyst are preferable. Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, , 3,4-xylenol, 3,5-xylenol, p-ethylphenol, p-isopropylphenol, p-tertiarybutylphenol, p-chlorophenol and p- . As the aldehydes, in addition to formalin, a formaldehyde generating material such as paraformaldehyde, trioxane, and tetraoxane may be used.

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

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

In the 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, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, More preferably a methyl group, an ethyl group, a propyl group or an allyl group, still more preferably a methyl group. R ₄ and R ₅ are each independently hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms, preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms More preferably a methyl group, an ethyl group, a propyl group or an allyl group, still more preferably a methyl group.

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

In the formula (1), X is selected from an epoxy resin or a phenol resin, more preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a bisphenol S type epoxy resin, Is selected. More specifically, X may be represented by the following formula (2) or (3).

(In the formula, n represents 1 to _10. R ₆ independently represents hydrogen, a methyl group, a phenyl group, or a trifluoromethyl group)

(In the formula, the * addition bonds with the O atom)

Examples of commercially available trifunctional alkoxysilane-modified resins include "E201" (epoxy equivalent 285 manufactured by Arakawa Chemical Industries, Ltd.) represented by the following formula (4), "P501" represented by the following formula Manufactured by Arakawa Chemical Industries, Ltd., phenolic hydroxyl group equivalent 275).

(Wherein n represents 1 to 10 and m represents 1 to 10)

(Wherein m represents 1 to 10)

<(C) Inorganic filler>

The inorganic filler (C) used in the present invention is not particularly limited, and examples thereof include silica, alumina, barium sulfate, talc, cray, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, , Aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among them, silica is preferable. Further, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica and hollow silica is preferable, and fused silica is more preferable. The silica is preferably spherical. These may be used alone or in combination of two or more. As commercially available spherical fused silica, "SOC2" and "SOC1" manufactured by Admatech Co., Ltd. can be mentioned.

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 preferably 5 占 퐉 or less, more preferably 3 占 퐉 or less, from the viewpoint of forming a fine wiring on the insulating layer, More preferably 1 mu m or less, still more preferably 0.7 mu m or less, particularly preferably 0.5 mu m or less, particularly preferably 0.4 mu m or less, and particularly preferably 0.3 mu m or less. On the other hand, the lower limit of the average particle diameter of the inorganic filler is preferably not less than 0.01 mu m, more preferably not more than 0.03 mu m, from the viewpoint of increasing the viscosity of the varnish and preventing the handling property from lowering, More preferably at least 0.05 mu m, even more preferably at least 0.05 mu m, particularly preferably at least 0.07 mu m, even more preferably at least 0.1 mu m. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured by using a laser diffraction particle size distribution measuring apparatus, and the median diameter of the inorganic filler is determined to be an average particle diameter. The measurement sample can be preferably those in which an inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction particle size distribution measuring apparatus, LA-500, 750, 950 and the like manufactured by Horiba Seisakusho Co., Ltd. can be used. The present invention uses LA-750.

The content of the inorganic filler in the resin composition is preferably from 20 to 85% by mass, more preferably from 30 to 80% by mass, more preferably from 30 to 80% by mass, , More preferably from 40 to 75 mass%, still more preferably from 50 to 70 mass%. If the content of the inorganic filler is too small, the coefficient of thermal expansion of the cured product tends to be high. If the content is too large, the cured product tends to become weak and the peel strength tends to decrease.

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

In the present specification, the "reaction" between the trifunctional alkoxysilane-modified resin (B) and the inorganic filler (C) means the reaction between the alkoxy group of the trifunctional alkoxysilane-modified resin (B) Condensation reaction, specifically concreting the hydrolysis / dehydration condensation reaction and the alcohol condensation reaction. Thus, the "reactant" in which the trifunctional alkoxysilane-modified resin (B) is formed by reacting with the inorganic filler (C) refers to a condensate of the trifunctional alkoxysilane-modified resin (B) and the inorganic filler (C) . In such a condensate, the trifunctional alkoxysilane-modified resin (B) is covalently bonded to the surface of the inorganic filler (C).

The inorganic filler (C) in which at least a part of the inorganic filler (C) or the trifunctional alkoxysilane-modified resin (B) of the present invention reacts to form a reactant is not particularly limited as long as the effect It is preferable that the surface treatment is performed with a surface treating agent such as a silane coupling agent, an aminosilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, or a titanate coupling agent to improve the moisture resistance . These may be used alone or in combination of two or more. Specific examples of the surface treatment agent include aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-2 (aminoethyl) aminopropyltrimethoxysilane , Glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxy Epoxysilane coupling agents such as cyclohexyltrimethoxysilane and cyclohexyltrimethoxysilane, mercaptosilane coupling agents such as mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane, methyltrimethoxysilane and octadecyltrimethoxysilane, Silane coupling agents such as silane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole silane, and triazinilane, hexamethyldisilazane, hexaphenyldisilazane, trisilazane, Organosilazane compounds such as chlorotrisilazane and 1,1,3,3,5,5-hexamethylcyclotrisilazane, butyl titanate dimers, titanium octylen glycolate, diisopropoxytitanium bis (triethanol Aminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl bis (dioctylphosphite) titanate, tetraoctyl bis (ditridecylphosphite) (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyltri octanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearate in Isopentyldodecylbenzenesulfonyltitanate, isopentyldodecylbenzenesulfonyltitanate, isopropyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltrimethoxysilane, And titanate-based coupling agents such as propyl tris (dioctyl pyrophosphate) titanate and isopropyl tri (N-amide ethyl aminoethyl) titanate.

Among them, the use of (C) an inorganic filler surface-treated with an organosilazane compound is advantageous from the viewpoints of improving the dispersibility of the resin varnish and improving the covering ratio of the inorganic filler by the trifunctional alkoxysilane-modified resin . Especially, hexamethyldisilazane is preferable. On the other hand, in the case of using the inorganic filler (C) surface-treated with the surface treatment agent, the (B) trifunctional alkoxysilane-modified resin may be covalently bonded to the surface of the inorganic filler (C) through the surface treatment agent.

In the resin composition of the present invention, the trifunctional alkoxysilane-modified resin (B) and the inorganic filler (C) may be directly added to the resin composition, and the trifunctional alkoxysilane-modified resin (B) and the inorganic filler It may be added after the reaction. It is preferable that the trifunctional alkoxysilane-modified resin (B) and the inorganic filler (C) are reacted in advance before being added to the resin composition in terms of improving the dispersibility in the resin composition. (B) the trifunctional alkoxysilane-modified resin (B) and the inorganic filler (C) are added to the resin composition in advance, at least a part of the trifunctional alkoxysilane-modified resin (B) A resin composition which reacts with the filler to form a reactant can be suitably obtained. Examples of the method of reacting the trifunctional alkoxysilane-modified resin (B) and the inorganic filler (C) in advance include the following methods.

(B) the trifunctional alkoxysilane-modified resin is mixed with MEK in advance, (C) the inorganic filler is stirred for 5 to 30 minutes, and the mixture is stirred at 50 to 150 占 폚 For 0.5 to 3 hours. More preferably, the mixture is stirred at 55 to 130 占 폚 for 0.5 to 3 hours, more preferably at 60 to 110 占 폚 for 0.5 to 3 hours, and still more preferably at 70 to 80 占 폚 for 1 to 3 hours. And thereafter, the volatile component is removed. In addition to the rotary mixer, a drum mixer, a rocking mixer, a vibrating fluidized bed, a powder dryer, or the like can be used, but a rotary mixer is preferable in that it can be easily performed. As the rotary mixer, there can be mentioned a Henschel type hornblender.

The content of the trifunctional alkoxysilane-modified resin (B) is preferably 5% by mass or less, more preferably 4% by mass or less based on 100% by mass of the inorganic filler (C) from the viewpoint of preventing the increase in melt viscosity , More preferably 3 mass% or less. Further, from the viewpoint of improving the dispersibility of the resin varnish, 0.1 mass% or more is preferable, 0.5 mass% or more is more preferable, and 1 mass% or more is more preferable.

The peel strength between the conductor layer and the insulating layer obtained by curing the resin composition of the present invention to form an insulating layer, roughening the surface of the insulating layer, and plating the surface of the insulating layer has the following relationship: peel strength ) &Gt; of the present invention.

The upper limit of the peel strength is preferably 0.7 kgf / cm or less, more preferably 0.8 kgf / cm or less, even 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 higher, more preferably 0.48 kgf / cm or higher, and still more preferably 0.53 kgf / cm or higher.

The arithmetic mean roughness (Ra value) and the root mean square roughness (Rq value) of the resin composition of the present invention after curing the insulating layer to form an insulating layer and roughening the surface of the insulating layer are determined by the following arithmetic mean roughness (Ra value), and the root-mean-square roughness (Rq value) of the root mean square value &gt;.

The upper limit of the arithmetic mean 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, particularly preferably 190 nm or less More preferably 170 nm or less, and particularly 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 further preferably 10 nm or more.

The upper limit of the root mean square roughness (Rq value) of the root mean square 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, More preferably 330 nm or less, particularly preferably 300 nm or less, and particularly preferably 250 nm or less. The lower limit of the root mean square roughness (Rq value) is preferably 90 nm or more, more preferably 70 nm or more, still more preferably 50 nm or more, still more preferably 30 nm or more, and particularly preferably 10 nm or more .

<(D) Curing accelerator>

By further containing a curing accelerator, the resin composition of the present invention can efficiently cure the epoxy resin and the curing agent. The curing accelerator is not particularly limited, and examples thereof include amine curing accelerators, guanidine curing accelerators, imidazole curing accelerators, phosphonium curing accelerators, and metal curing accelerators. These may be used alone or in combination of two or more.

Examples of amine curing accelerators include, but are not limited to, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) And amine compounds such as 1,8-diazabicyclo (5,4,0) -undecene (hereinafter referred to as DBU). These may be used alone or in combination of two or more.

Examples of the guanidine curing accelerator include, but are not limited to, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, Phenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4. 0] deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide and 1- (o-tolyl) biguanide. These may be used alone or in combination of two or more.

Examples of the imidazole-based curing accelerator include, but are not limited to, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, Methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- methylimidazole, 2-phenylimidazole, Methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- Diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- 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-5hydroxymethylimidazole, 2-methylimidazolium chloride, 2-methylimidazoline, 2-phenyl-2-methylimidazolium chloride, 2- Imidazole compounds such as imidazole and imidazole compounds and adducts with an epoxy resin. These may be used alone or in combination of two or more.

Examples of the phosphonium curing accelerator include, but are not limited to, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. These may be used alone or in combination of two or more.

In the resin composition of the present invention, the content of the curing accelerator (excluding the metal curing accelerator) is preferably in the range of 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, The range of mass% is more preferable. If the amount is less than 0.005 mass%, the curing will be delayed and the thermosetting time tends to be long. When the amount is more than 1 mass%, the storage stability of the resin composition tends to decrease.

The metal-based curing accelerator is not particularly limited, and examples thereof include organometallic complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc An organic iron complex such as an organic zinc complex and iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used singly or in combination of two or more.

In the resin composition of the present invention, the addition amount of the metal-based curing accelerator is preferably in the range of 25 to 500 ppm based on the metal-based curing catalyst when the nonvolatile component in the resin composition is 100 mass% A range of 200 ppm is more preferable. If it is less than 25 ppm, it tends to make it difficult to form a conductor layer having a low arithmetic mean roughness with good adhesion to the surface of the insulating layer. If it exceeds 500 ppm, the storage stability and insulating properties of the resin composition tend to be lowered.

<(E) Curing agent>

The resin composition of the present invention can further improve the insulating property and mechanical properties by containing a curing agent. Examples of the curing agent (E) include, but are not limited to, phenolic curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, cyanate ester curing agents and acid anhydride curing agents, Phenol-based curing agent, naphthol-based curing agent and active ester-based curing agent are preferable from the viewpoint of lowering the value of the curing agent. These may be used alone or in combination of two or more.

Examples of the phenol-based curing agent and naphthol-based curing agent include, but are not limited to, phenol-based curing agents having a novolac structure and naphthol-based curing agents having a novolac structure, and phenol novolac resins, phenazine novolac resins containing a triazine skeleton, Naphthol novolak resin, naphthol aralkyl type resin, triazine skeleton-containing naphthol resin and biphenyl aralkyl type phenol resin are preferable. Examples of commercially available products include biphenyl aralkyl phenol resins such as "MEH-7700", "MEH-7810", "MEH-7851", "MEH7851-4H" (manufactured by Meiwa- SN170 "," SN180 "," SN190 "," SN190 ", and" SN190 "as naphthol aralkyl type resins are used as the naphthol novolac resin," NHN "," CBN "(manufactured by Nippon Kayaku Co., SN405 "(manufactured by DIC Corporation) as a phenol novolak resin, phenol novolac containing a triazine skeleton," SN455 "," SN495 "," SN495 " LA3018 "," LA7052 "," LA7054 ", and" LA1356 "(manufactured by DIC Corporation). These may be used alone or in combination of two or more.

The active ester-based curing agent is not particularly limited, but generally, an ester group having high reactivity such as esters of phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds is used in an amount of 2 Is preferably used. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. From the viewpoint of heat resistance improvement, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type curing agent obtained from a carboxylic acid compound, a phenol compound and / or a naphthol compound is more preferable. Examples of the phenolic compound or the naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol A, and the like. Examples of the phenolic compound and the naphthol compound include benzoic acid, benzoic acid, acetic acid, Methylene bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, alpha -naphthol, beta -naphthol, 1,5-bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, Examples of the active ester-based curing agent may include one or more selected from the group consisting of active ester-based curing agents, curing accelerator-based curing agents, As the curing agent, the active ester curing agent disclosed in Japanese Patent Application Laid-Open No. 2004-277460 may be used, or a commercially available active ester curing agent may be used. As the commercially available active ester curing agent, a dicyclopentadienyldiphenol structure Acetylated phenol novolak, benzoylated phenol novolak, and the like. Among them, those containing a dicyclopentadienyldiphenol structure are more preferable. Specifically, a dicyclopentadienyldiphenol structure EXB9460S, EXB9460S-65T and HPC-8000-65T (manufactured by DIC Corporation, having an active equivalent weight of about 223), phenol novolak acetylates , YLH1026 (manufactured by Japan Epoxy Resin Co., Ltd., active group equivalent of about 200), YLH1030 (manufactured by Japan Epoxy Resin Co., Ltd., trade name, manufactured by Japan Epoxy Resins Co., And YLH1048 (manufactured by Japan Epoxy Resins Co., Ltd., active group equivalent of about 245). Among them, EXB9460S is preferable from the viewpoint of storage stability of varnish and thermal expansion coefficient of cured product.

More specifically, examples of the active ester-based curing agent containing a dicyclopentadienyldiphenol structure include those represented by the following formula (6).

(Wherein R represents a phenyl group or a naphthyl group, k represents 0 or 1, and n represents an average of the repeating units of 0.05 to 2.5)

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

Examples of the benzoxazine-based curing agent include, but are not particularly limited to, F-a, P-d (manufactured by Shikoku Chemicals) and HFB2006M (manufactured by Showa Kobunshi Co., Ltd.).

Examples of the cyanate ester curing agent include, but are not limited to, novolac (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type curing agent, dicyclopentadiene type cyanate ester type curing agent, bisphenol type Bisphenol F, bisphenol S, etc.) cyanate ester curing agents, and partially triarylated prepolymers thereof. The weight average molecular weight of the cyanate ester curing agent is not particularly limited, but is preferably 500 to 4500, more preferably 600 to 3000. Specific examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1- Cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis Bifunctional cyanate resins such as phenol novolak, cresol novolac, and dicyclopentadiene structure-containing phenolic resins, and the like. These multifunctional cyanate resins, And a prepolymer obtained by partially nitrating a nate resin. These may be used singly or in combination of two or more kinds. Examples of commercially available cyanate ester resins include phenol novolac type polyfunctional cyanate ester resins (PT30, cyanate equivalent 124, manufactured by Lone Japan Co., Ltd.) represented by the following formula (7) (BA230, cyanate equivalent weight 232, manufactured by Lone Japan Co., Ltd.) in which some or all of the eluted bisphenol A dicyanate is triarized to form a trimer, a dicyclopentadiene structure-containing cyanate represented by the following formula (9) Ester resin (DT-4000, DT-7000, manufactured by Lone Japan Co., Ltd.).

[Wherein n represents an arbitrary number (preferably 0 to 20) as an average value]

(In the formula, n represents an average value of 0 to 5)

Examples of the acid anhydride-based curing agent include, but are not limited to, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, Dodecenyl anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, anhydrous trimellitic anhydride Examples of the anion selected from the group consisting of acetic anhydride, acetic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'- Carboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,3-dione, ethylene glycol bis (anhydrotrimellitate), styrene-maleic acid copolymer Butylene, and the like of the polymer-type acid anhydrides such as maleic acid resin.

In the resin composition of the present invention, from the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition, the ratio of (A) the total number of epoxy groups in the epoxy resin to the total number of reactors in the (E) Preferably 0.2 to 2, more preferably 1: 0.3 to 1.5, further preferably 1: 0.4 to 1. On the other hand, the total number of epoxy groups in the epoxy resin present in the resin composition is a value obtained by dividing the solid component mass of each epoxy resin by the epoxy equivalent, for all epoxy resins, and the total number of reactors of the curing agent The value obtained by dividing the mass by the equivalent of the reactor is the sum of all the curing agents.

&Lt; (F) Thermoplastic resin >

The resin composition of the present invention can further improve the mechanical strength of the cured product by further containing (F) a thermoplastic resin, and also improve the film formability when it is used in the form of an adhesive film. Examples of the thermoplastic resin include phenoxy resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyether sulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, Resin. These thermoplastic resins may be used alone or in combination of two or more. The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000. If it is smaller than this range, the effect of improving film formability and mechanical strength tends not to be sufficiently exhibited. If it is larger than this range, compatibility with the cyanate ester resin and naphthol type epoxy resin is not sufficient and surface unevenness after curing becomes large , It tends to be difficult to form a high-density fine wiring. Meanwhile, the weight average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). Specifically, the weight average molecular weight by the GPC method was measured using LC-9A / RID-6A manufactured by Shimadzu Corporation, Shodex K-800P / K-2 manufactured by Showa Denko K.K., 804L / K-804L can be measured at a column temperature of 40 占 폚 using chloroform or the like as a mobile phase, using a calibration curve 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 to 10% by mass relative to 100% by mass of the non- , More preferably from 1 to 5 mass%. If the content of the thermoplastic resin is too small, the effect of improving film formability and mechanical strength tends not to be exhibited. If the content is too large, the melt viscosity tends to increase and the arithmetic average roughness of the surface of the insulating layer after the wet coarsening step tends to increase.

<(G) Rubber particles>

By further containing (G) rubber particles, the resin composition of the present invention can improve the plating peel strength, improve the drilling workability, lower the dielectric tangent, and obtain the stress relaxation effect. The rubber particles that can be used in the present invention are not dissolved in the organic solvent used for preparing the varnish of the resin composition, and are not compatible with cyanate ester resin, epoxy resin or the like as essential components. Therefore, the rubber particles are present in a dispersed state in the varnish of the resin composition of the present invention. These rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which the rubber component is insoluble in an organic solvent or a resin, thereby forming a granular phase.

Preferred examples of the rubber particles usable in the present invention include core-shell rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles and the like. The core-shell-type rubber particles are rubber particles having a core layer and a shell layer. For example, the core-shell rubber particle may be a two-layer structure in which the shell layer of the outer layer is composed of a glassy polymer and the core layer of the inner layer is composed of a rubbery polymer, Layer structure in which the intermediate layer is made of a rubber-like polymer and the core layer is made of a glass-like polymer, and the like. The glassy polymer layer is composed of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is composed of, for example, a 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 include star filloids AC3832, AC3816N, IM-401 1, IM-401 7-17 (trade name, manufactured by Gansu Kasei Corporation), Metablen KW-4426 (trade name, Mitsubishi Rayon Ltd.). Specific examples of crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle diameter 0.5 mu m, manufactured by JSR Corporation). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle size: 0.5 탆, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include Metablen W300A (average particle diameter 0.1 mu m) and W450A (average particle diameter 0.2 mu m) (manufactured by Mitsubishi Rayon Co., Ltd.).

The average particle diameter of the rubber particles to be blended is preferably in the range of 0.005 to 1 mu m, more preferably in the range of 0.2 to 0.6 mu m. 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 ultrasonic waves or the like, and the particle size distribution of the rubber particles is prepared on the mass basis using a rich system particle size analyzer (FPAR-1000, manufactured by Otsuka Denshi Co., Ltd.) The measurement can be made by setting the methane diameter to the average particle diameter.

The content of the rubber particles is preferably from 1 to 10% by mass, more preferably from 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 retardant. Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. Examples of the organophosphorus flame retardant include phenanthrene-type phosphorus compounds such as HCA, HCA-HQ and HCA-NQ manufactured by Sanko Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Kobunshi Co., TPPO, TPPO, BPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, manufactured by Hokokagakukogyo Co., PPO, OP930 manufactured by Clariant Co., Ltd. and PX200 manufactured by Daihachi Chemical Co., Ltd., phosphorus-containing epoxy resin such as FX289, FX305, and TX0712 manufactured by Toto Kasei Co., Ltd., ), Phosphorus-containing phenoxy resins such as ERF001, and phosphorus-containing epoxy resins such as YL7613 (manufactured by Japan Epoxy Resin Co., Ltd.). Examples of the organic nitrogen-containing phosphorus compound include phosphate ester amide compounds such as SP670 and SP703 manufactured by Shikoku Kasei Corporation, SPB100, SPE100 manufactured by Otsuka Kasei Co., Ltd. and FP-series manufactured by Fushimi Fine Chemical Co., Prazene compounds and the like. Examples of the metal hydroxide include magnesium hydroxide such as UD65, UD650 and UD653 manufactured by Ube Industries, Ltd., B-30, B-325, B-315, B-308 and B-303 manufactured by Tomoe Kogyo Co., , Aluminum hydroxide such as UFH-20, and the like.

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

<Other Ingredients>

In the resin composition of the present invention, other components may be blended as necessary within the range not hindering the effect of the present invention. Examples of the other components include thermoplastic resins such as vinyl benzyl compounds, acrylic compounds, maleimide compounds and block isocyanate compounds, organic fillers such as silicone powder, nylon powder and fluorine powder, thickeners such as orthobenzene and benzene, A coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, carbon black, etc. may be added to the composition of the present invention in the presence of an antifoaming agent or a leveling agent of an imidazole, thiazole, triazole or silane coupling agent .

The method for preparing the resin composition of the present invention is not particularly limited and includes, for example, a method in which a solvent or the like is added, if necessary, followed by mixing using a rotary mixer or the like.

The use of the resin composition of the present invention is not particularly limited, but the resin composition of the present invention can be used in the form of an insulating resin sheet such as an adhesive film or a prepreg, a circuit board (laminate board, multilayer printed wiring board, etc.), a solder resist, an underfill material, It can be widely used in applications where a resin composition is required such as a filler resin, a component-embedded resin, and the like. In particular, in the production of a multilayered printed circuit board, a resin composition for forming an insulating layer (a resin composition for an insulating layer of a multilayer printed circuit board) can be suitably used, and a resin composition for forming a conductor layer by plating (A resin composition for an insulating layer of a multilayered printed circuit board which forms a conductor layer), and can more suitably be used as a resin composition (a resin composition for a build-up layer of a multilayer printed wiring board) for forming a buildup layer. The resin composition of the present invention may be applied to a circuit board in a varnish state to form an insulating layer, but industrially, it is generally preferable to use it in the form of a sheet-like laminate material such as an adhesive film or a prepreg. The softening point of the resin composition is preferably 40 to 150 DEG C from the viewpoint of the lamination property of the sheet-like laminated material.

&Lt; Adhesive film &

The adhesive film of the present invention can be produced by a method known to those skilled in the art, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, applying the resin varnish to a support using a die coater or the like, And then drying the organic solvent by spraying or the like to form a resin composition layer.

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

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

The thickness of the resin composition layer formed in the adhesive film is preferably not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 mu m, the resin composition layer preferably has a thickness of 10 to 100 mu m.

Examples of the support include films of polyolefins such as polyethylene, polypropylene and polyvinyl chloride, films of polyester such as polyethylene terephthalate (hereinafter may be abbreviated as "PET"), polyethylene naphthalate, polycarbonate film, polyimide film And the like. In addition, a metal foil such as an aluminum foil, a copper foil or an aluminum foil may be used. The support and the protective film to be described later may be subjected to a surface treatment such as a mat treatment or a corona treatment. In addition, the releasing treatment may be carried out with a releasing agent such as a silicone resin-based releasing agent, an alkyd resin-based releasing agent, or a fluororesin-based releasing agent.

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

On the surface of the resin composition layer on which the support is not closely adhered, a protective film corresponding to the support can be further laminated. The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 탆. By laminating a protective film, it is possible to prevent adhesion and scratches of dust on the surface of the resin composition layer. The adhesive film may be rolled up and stored.

<Multilayer Printed Circuit Board Using Adhesive Film>

Next, an example of a method for producing a multilayered printed circuit board using the adhesive film produced as described above will be described.

First, the adhesive film is laminated on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. On the other hand, the circuit board here means a patterned conductor layer (circuit) formed on one or both sides of the substrate. In the multilayered printed circuit board in which the conductor layer and the insulating layer are alternately laminated, the circuit board includes the outermost layer of the multilayered printed circuit board in which one or both sides are patterned conductor layers (circuits) . On the other hand, the surface of the conductor layer may be previously roughened by blackening treatment, copper etching, or the like.

In the laminate, if the adhesive film has a protective film, the protective film is removed, and if necessary, the adhesive film and the circuit board are preheated, and the adhesive film is pressed on the circuit board while being pressed and heated. In the adhesive film of the present invention, a method of laminating a circuit substrate under reduced pressure by a vacuum laminating method is suitably used. The lamination conditions are not particularly limited. For example, the pressing temperature (lamination temperature) is preferably 70 to 140 占 폚, and the pressing pressure is preferably 1 to 11 kgf / cm2 (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m &lt; 2 &gt;) and laminated under a reduced pressure of 20 mmHg (26.7 hPa) or less. The lamination method may be a batch method or a roll type continuous method. Vacuum laminates can be made using commercially available vacuum laminators. As a commercially available vacuum laminator, there can be mentioned, for example, a vacuum applicator manufactured by Nichigo Morton Co., Ltd., a vacuum pressurized laminator manufactured by Meiji Seisakusho Co., Ltd., a roll type dry coater manufactured by Hitachi Industries Co., Ltd., Manufacturing vacuum laminator, and the like.

The lamination step for heating and pressurizing under reduced pressure can also be carried out using a general vacuum hot press machine. For example, a metal plate such as a heated SUS plate can be pressed on the support layer side. The pressing condition is such that the reduced pressure is usually 1 x ^10-2 MPa or less, preferably 1 x ^10-3 MPa or less. Heating and pressurization can be carried out in one step, but it is preferable to divide the conditions into two or more steps from the viewpoint of controlling the penetration of the resin. For example, the first-stage press is performed at a temperature of 70 to 150 ° C, a pressure of 1 to 15 kgf / cm 2, a second-stage press at a temperature of 150 to 200 ° C and a pressure of 1 to 40 kgf / . The time for each step is preferably 30 to 120 minutes. Examples of commercially available vacuum hot presses include MNPC-V-750-5-200 (manufactured by Meikisha Chemical Co., Ltd.) and VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.).

After the adhesive film is laminated on the circuit board and then cooled to about room temperature, when the support is peeled off, the insulating film can be formed on the circuit board by peeling and thermosetting. The conditions of the thermosetting may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 20 to 180 minutes at 150 to 220 deg. C, more preferably 30 to 30 minutes at 160 to 210 deg. 120 minutes.

After forming the insulating layer, if the support is not peeled off before curing, peel off here. Then, if necessary, a hole is formed in the insulating layer formed on the circuit board to form a via hole and a through hole. The drilling can be performed by a known method such as drilling, laser, plasma or the like, or by combining these methods as necessary. However, boring by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method.

Subsequently, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, known 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 subjected to a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order to form an unevenness anchor. The swelling treatment with the swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50 to 80 캜 for 5 to 20 minutes. Examples of the swelling solution include an alkaline solution and a surfactant solution, and preferably an alkaline solution. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securiganth P and Swelling Dip Securiganth SBU manufactured by Atotech Japan Co., . The roughening treatment with an oxidizing agent is carried out by immersing the insulating layer in an oxidizing agent solution at 60 ° C to 80 ° C for 10 minutes to 30 minutes. Examples of the oxidizing agent include an alkaline permanganic acid solution prepared 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. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10 wt%. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd., and Dozing Solution S Curegan's P and the like. The neutralization treatment by the neutralization liquid is carried out by immersing in the neutralization liquid at 30 to 50 캜 for 3 to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferable, and commercially available products include Reduction Solution · Sucrygant P manufactured by Atotech Japan Co., Ltd.

Subsequently, a conductor layer is formed by combining electroless plating and electrolytic plating. Alternatively, a plating resist having an inverse pattern to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method of forming the pattern thereafter, for example, a subtractive method, a semiadditive method, and the like known to those skilled in the art can be used.

<Prepreg>

The prepreg of the present invention can be produced by impregnating the resin composition of the present invention with a sheet type reinforcing base material made of fibers by a hot-melt method or a solvent method, and heating and semi-curing the resin composition. That is, the resin composition of the present invention can be used as a prepreg which is in a state impregnated with a sheet-like reinforcing base material made of fibers. As the sheet-like reinforcing base material made of fibers, for example, those made of fibers commonly used as prepreg fibers such as glass cloth and aramid fibers can be used.

The hot-melt method is a method in which a resin is not dissolved in an organic solvent but is once coated on a coated paper having good releasability to the resin and laminated on the sheet type reinforcing base material or the resin is dissolved in an organic solvent, Or directly applied to a reinforcing base material to form a prepreg. The solvent method is a method in which a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as an adhesive film, the sheet type reinforcing base material is immersed in the varnish, the resin varnish is impregnated into the sheet type reinforcing base material, to be.

<Multilayer Printed Circuit Board Using Prepreg>

Next, an example of a method for producing a multilayered printed circuit board using the prepreg produced as described above will be described. One prepreg of the present invention or several sheets of the prepreg of the present invention are overlaid on the circuit board, sandwiched between the metal plates with the release film interposed therebetween, and vacuum press laminated under pressure and heating conditions. The pressing and 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 min. Further, similarly to the adhesive film, it is also possible to laminate the prepreg on the circuit board by the vacuum lamination method, followed by heating and curing. Thereafter, in the same manner as the above-described method, after the surface of the cured prepreg is roughened, a conductor layer is formed by plating to produce a multilayer printed wiring board.

<Semiconductor Device>

The semiconductor device can be manufactured by using the multilayered printed circuit board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of the multilayered printed circuit board of the present invention. The &quot; conduction site &quot; is a &quot; site where electric signals are transmitted in the multilayered printed circuit board &quot;, and the site may be a surface or a buried site. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor material.

The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip effectively functions. Specifically, the semiconductor chip mounting method, the flip chip mounting method, the bump- (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a nonconductive film (NCF).

Refers to a mounting method in which a semiconductor chip is directly buried in a concave portion of a multilayer printed wiring board to connect the semiconductor chip and the wiring on the printed wiring board to each other. The BBUL method 1), and the BBUL method 2).

BBUL Method 1) A mounting method for mounting a semiconductor chip on a concave portion of a multilayer printed wiring board using an underfill

BBUL method 2) A mounting method for mounting a semiconductor chip on a concave portion 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 conductor layer is removed from both sides of the multilayer printed wiring board, and through holes are formed by a laser or a mechanical drill.

Step 2) An adhesive tape is adhered to one surface of the multilayer printed wiring board so that the bottom surface of the semiconductor chip is fixed on the adhesive tape in the through hole. It is preferable that the semiconductor chip at this time be made lower than the height of the through hole.

Step 3) An underfill is injected and filled in the gap between the through hole and the semiconductor chip, thereby fixing the semiconductor chip to the through hole.

Step 4) Thereafter, the adhesive tape is peeled to expose the bottom surface of the semiconductor chip.

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

Step 6) After the adhesive film or the prepreg is cured, holes are drilled by laser to expose the bonding pads on the bottom surface of the semiconductor chip, and the roughening treatment, the electroless plating and the electrolytic plating are performed as described above, . If necessary, an adhesive film or prepreg may be further laminated.

The BBUL method 2) specifically includes the following steps.

Step 1) A photoresist film is formed on the conductor layers on both surfaces of the multilayer printed wiring board, and openings are formed on only one side of the photoresist film by photolithography.

Step 2) The conductor layer exposed in the opening is removed by an etching solution to expose the insulating layer, and then the resist film on both sides is removed.

Step 3) By using a laser or a drill, the exposed insulating layer is completely removed and the hole is drilled to form a concave portion. The energy of the laser is preferably a laser capable of adjusting the energy so as to lower the laser absorption rate of copper and increase the laser absorption rate of the insulating layer, and a carbon dioxide gas laser is more preferable. By using such a laser, it is possible to remove only the insulating layer without penetrating the conductor layer on the opposite side of the opening portion of the conductor layer.

Step 4) The bottom surface of the semiconductor chip is disposed in the concave portion with the opening facing the opening, and the adhesive film or the prepreg of the present invention is laminated on the opening side to cover the semiconductor chip to fill the gap between the semiconductor chip and the concave portion. It is preferable that the semiconductor chip at this time be made lower than the height of the recess.

Step 5) After the adhesive film or the prepreg is cured, it is perforated with a laser to expose the bonding pad on the bottom surface of the semiconductor chip.

Step 6) The roughening treatment, the electroless plating, and the electrolytic plating shown above are performed to connect the wirings and further laminate an adhesive film or a prepreg if necessary.

Among the semiconductor chip mounting methods, there is a viewpoint of miniaturization of the semiconductor device and reduction of the transmission loss. However, since the solder is not used, the thermal history of the semiconductor chip is insufficient and the twist of the solder and the resin can not be caused in the future , The BBUL method 1) and the BBUL method 2) are more preferable, and the BBUL method 2) is more preferable.

Example

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples.

<Methods of measurement and evaluation>

First, various measurement methods and evaluation methods will be described.

&Lt; Preparation of sample for measurement of peel strength and arithmetic average roughness (Ra value) and root mean square roughness (Rq value)

(1) ground treatment of inner layer circuit board

Both surfaces of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 탆, substrate thickness 0.3 mm, substrate R5715ES manufactured by Matsushita Electric Industrial Co., Ltd.) having an inner layer circuit were etched with CZ8100, Harmonious treatment was performed.

(2) Laminate of adhesive film

The adhesive films prepared in Examples and Comparative Examples were laminated on both surfaces of an inner layer circuit board using a batch vacuum pressure laminator MVLP-500 (trade name, manufactured by Meikyu Corporation). The laminate was pressed by depressurization for 30 seconds, setting the air pressure to 13 hPa or less, and then pressing it at 100 DEG C and 0.74 MPa for 30 seconds.

(3) Curing of resin composition

The laminated adhesive film was peeled off for PET films of Examples 1 to 4, and then the resin composition was cured at 100 캜 for 30 minutes at 180 캜 for 30 minutes under the same conditions as in Example 5 After thermally curing, the PET film was peeled off to form an insulating layer.

(4) Harmonization processing

An inner layer circuit board having an insulating layer formed thereon was subjected to Swelling Diff · Sucry Gant P (glycol ether, aqueous solution of sodium hydroxide) containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd., which is a swelling liquid, The samples were immersed for 10 minutes at 60 占 폚 for 10 minutes and 60 占 폚 for Example 5. Subsequently, Concentrate Compact P (KMnO4: 60 g / L, manufactured by Atotech Japan Co., (Aqueous solution of NaOH: 40 g / L) for 15 minutes at 80 DEG C for Example 1 and 20 minutes at 80 DEG C for Example 5, and as a neutralization liquid, the reduction of Atotech Japan Co., The solution was immersed in a solution of sucyrant P (glyoxal, aqueous solution of sulfuric acid) at 40 ° C for 5 minutes. After drying at 80 캜 for 30 minutes, arithmetic mean roughness (Ra value) and square mean square roughness (Rq value) of the surface of the insulating layer after the coarsening treatment were measured.

(5) Plating by semi-additive method

To form a circuit on the surface of the insulating layer, the inner-layer circuit board was immersed in a solution for electroless plating containing PdCl ₂ at 40 ° C for 5 minutes and then immersed in electroless copper plating solution at 25 ° C for 20 minutes. An annealing treatment was performed at 150 占 폚 for 30 minutes to form an etching resist, a pattern was formed by etching, and copper sulfate electroplating was performed to form a conductor layer with a thickness of 35 占 퐉. Then, the annealing treatment was performed at 200 DEG C for 60 minutes. The peeling strength (peeling strength) of the plated conductor layer was measured on this circuit board.

&Lt; Measurement of Peel Strength (Peel Strength) of Plated Conductor Layer >

A partial cut slit having a width of 10 mm and a length of 100 mm was put in the conductor layer of the circuit board and the slit was peeled off and held with a gripper (TESUI Corporation, auto-comb type tester AC-50C-SL) And the load (kgf / cm) at the time of peeling 35 mm in the vertical direction at the speed was measured.

&Lt; Measurement of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) after harmonization >

The Ra value and the Rq value were obtained from the values obtained by setting the measurement range to 121 占 퐉 占 92 占 퐉 by the VSI contact mode and the 50x magnification lens using a non-contact surface roughing machine (WYKO NT3300 manufactured by Vico Instruments Inc.). Then, measurements were made by obtaining an average value of 10 points.

<Measurement of Average Thermal Expansion Rate and Glass Transition Temperature>

The adhesive films obtained in Examples and Comparative Examples were thermally cured by heating at 200 DEG C for 90 minutes, and the PET film was peeled off to obtain a sheet-like cured product. The cured product was cut into test pieces having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was carried out by the tensile weighting method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Corporation). After the test piece was mounted on the above apparatus, the test piece was continuously measured twice under the conditions of a load of 1 g and a heating rate of 5 캜 / min. The average coefficient of thermal expansion (ppm) from 25 deg. C to 150 deg. C in the second measurement was calculated. The glass transition temperature (占 폚) was calculated at the point where the slope of the dimensional change signal at the second measurement was changed.

&Lt; Preparation Example 1 &

100 parts by mass of spherical silica ("SOC2" manufactured by Admatex Co., Ltd., average particle diameter: 0.5 μm) was added to the hen-shell type hornblende to obtain a trifunctional alkoxysilane-modified resin ("E201" manufactured by Arakawa Chemical Industries, Epoxy equivalent 285) was mixed with 1.8 parts by mass of MEK in advance. The spherical silica was stirred for 10 minutes while spraying, and further stirred at 75 ° C for 1 hour. The volatile components were then removed to prepare a product 1.

&Lt; Preparation Example 2 &

100 parts by mass of spherical silica ("SOC2" manufactured by Admatex Co., Ltd., average particle diameter: 0.5 μm) was added to the hen-shell type mixed rhombic structure to obtain a trifunctional alkoxysilane-modified resin ("P501" manufactured by Arakawa Chemical Industries, Phenolic hydroxyl group equivalent: 275) was mixed with 1.8 parts by mass of MEK in advance. While stirring, the spherical silica was stirred for 10 minutes and further stirred at 75 ° C for 1 hour. Volatile components were then removed to prepare Preparation 2.

&Lt; Preparation Example 3 &

100 parts by mass of spherical silica ("SOC2" manufactured by Admatex Co., Ltd., average particle size: 0.5 μm) was added to the hen-shell type hornblende, and a tetrafunctional alkoxysilane-modified resin ("E202C" manufactured by Arakawa Chemical Industries, (10) shown below) and 1.8 parts by mass of epoxy equivalent 285 were mixed with 1.8 parts by mass of MEK in advance. The spherical silica was stirred for 10 minutes while spraying, stirred at 75 ° C for further 1 hour, .

(Wherein n represents 1 to 10 and m represents 1 to 10)

&Lt; Preparation Example 4 &

100 parts by mass of spherical silica ("SOC2" manufactured by Admatex Co., Ltd., average particle diameter: 0.5 μm) was added to the hen-shell type mixed rhombic ring and a tetrafunctional alkoxysilane-modified resin ("P502" manufactured by Arakawa Chemical Industries, , 1.8 parts by mass of phenolic hydroxyl group equivalent (300)) was mixed with 1.8 parts by mass of MEK in advance. The spherical silica was stirred for 10 minutes while spraying, and further stirred at 75 ° C for 1 hour. The volatile components were then removed, Production 4 was produced.

(Wherein m represents 1 to 10)

&Lt; Example 1 >

, 5 parts by mass of a naphthalene type epoxy resin (epoxy equivalent 144, "HP4700" manufactured by DIC Corporation), 14 parts by mass of a liquid bisphenol A type epoxy resin (epoxy equivalent 180, "jER828EL" manufactured by Mitsubishi Chemical Corporation) (Epoxy equivalent 269, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.) (14 parts by mass) was dissolved by heating in 30 parts by mass of solvent naphtha with stirring and then cooled to room temperature to prepare Mixture 1. Subsequently, 1.5 parts by mass of rubber particles (STABILLOID AC3816N, manufactured by Gansu Chemical Industry Co., Ltd.) was subjected to constant swelling at room temperature for 12 hours in 6 parts by mass of solvent naphtha to prepare Mixture 2. 100 parts by mass of spherical silica (&quot; SOC2 &quot; manufactured by Admatech Co., Ltd., average particle diameter 0.5 占 퐉) and 3 parts of a trifunctional alkoxysilane-modified resin ("E201" manufactured by Arakawa Chemical Industries, (Epoxy equivalent 285) as it is, and as a flame retardant ("HCA-HQ", 10- (2,5-dihydroxyphenyl) -10-hydro-9- -Phosphophenanthrene-10-oxide, average particle diameter 1 mu m) were added to the mixture, and the mixture was kneaded and dispersed in a three-roll mill. 10 parts by mass of a phenol novolak type curing agent ("LA-7054" manufactured by DIC Corporation, a solution of methyl ethyl ketone (hereinafter abbreviated as "MEK") having 60% by mass of nonvolatile content of phenolic hydroxyl group equivalent 124) 10 parts by mass of a naphthalene-based phenol resin (phenolic hydroxyl equivalent 215, "SN485" manufactured by Shinnets Tetsu Kagaku Co., Ltd., MEK solution of nonvolatile matter 60% by mass), 10 parts by mass of phenoxy resin (weight average molecular weight: 35,000, Mitsubishi Kagaku , 7 parts by mass of a solution of "YL7553" nonvolatile matter 30% by mass of MEK and cyclohexanone 1: 1), 2 parts by mass of a 5% by mass MEK solution of 4-dimethylaminopyridine as a curing accelerator, 2 parts by mass of methyl ethyl ketone (MEK) 4 parts by mass were mixed and uniformly dispersed with a rotary mixer to prepare a resin varnish. Subsequently, this resin varnish was uniformly applied on a releasable surface of a polyethylene terephthalate film (thickness: 38 mu m) treated with an alkyd type releasing treatment by means of a die coater so that the thickness of the resin composition layer after drying became 40 mu m, (Average 95 ° C) for 5 minutes (amount of residual solvent in the resin composition layer: about 2 mass%). Then, a polypropylene film having a thickness of 15 占 퐉 was adhered to the surface of the resin composition layer and rolled up into a roll. The roll-type adhesive film was slit with a width of 507 mm to obtain a sheet-like adhesive film of 507 x 336 mm in size.

&Lt; Example 2 >

, 1.8 parts by mass of a trifunctional alkoxysilane-modified resin ("E201" manufactured by Arakawa Chemical Industries, Ltd., epoxy equivalent 285) of Example 1 was mixed with a trifunctional alkoxysilane-modified resin ("P501" manufactured by Arakawa Chemical Industries, Quot ;, phenolic hydroxyl group equivalent 275) was changed to 1.8 parts by mass, a resin varnish was prepared in exactly the same manner. Using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

&Lt; Example 3 >

100 parts by mass of spherical silica ("SOC2" manufactured by Admatex Co., Ltd., average particle size: 0.5 μm) of Example 1, 10 parts by mass of a trifunctional alkoxysilane-modified resin ("E201" manufactured by Arakawa Chemical Industries, 285) were directly added to the resin varnish in the same manner as in Production Example 1 except that the product 1 was added. Using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

<Example 4>

100 parts by mass of spherical silica ("SOC2" manufactured by Admatex Co., Ltd., average particle size: 0.5 μm) of Example 1, 10 parts by mass of a trifunctional alkoxysilane-modified resin ("E201" manufactured by Arakawa Chemical Industries, 285) were directly added to the resin varnish in the same manner as in Production Example 1 except that the product 2 was added. Using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

&Lt; Example 5 >

, 8 parts by mass of a naphthalene type epoxy resin (epoxy equivalent 144, "EXA4032SS" manufactured by DIC Corporation) and 10 parts by mass of a beacilene type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 9 parts by mass of epoxy resin (epoxy equivalent of about 330, "ESN-475V", manufactured by Shinnittetsu Kagaku Co., Ltd.) was dissolved by heating in 33 parts by mass of solvent naphtha with stirring. After cooled to room temperature, 1.5 parts by mass of star fillyl (AC3816N, manufactured by GanTecha Chemical Co., Ltd.) as the rubber particles were added to 6 parts by mass of solvent naphtha for 12 hours at room temperature, ), 140 parts by mass of "SOC2" manufactured by Admatech Co., Ltd., average particle size of 0.5 μm), 1.4 parts by mass of a trifunctional alkoxysilane-modified resin ("P501" manufactured by Arakawa Chemical Industries, Ltd., phenolic hydroxyl equivalent of 275) And the mixture was kneaded and dispersed in a three-roll mill. Thereafter, 45 parts by mass of an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution of a nonvolatile matter having an equivalent weight of about 223 as an active ingredient and 65% by mass of a toluene solution), a phenoxy resin (weight average molecular weight: 35,000, , 5 parts by mass of a solution of "MEK (30% by mass of non-volatile matter, 1: 1 solution of cyclohexanone)" as a curing accelerator, 4 parts by mass of a 5% by mass MEK solution of 4-dimethylaminopyridine, MEK) were mixed and uniformly dispersed with a rotary mixer to prepare a resin varnish. Using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

&Lt; Comparative Example 1 &

Except that the trifunctional alkoxysilane-modified resin ("E201" manufactured by Arakawa Chemical Industries, Ltd., epoxy equivalent: 285) of Example 1 was not added. Using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

&Lt; Comparative Example 2 &

, 1.8 parts by mass of a trifunctional alkoxysilane-modified resin ("E201" manufactured by Arakawa Chemical Industries, Ltd., epoxy equivalent 285) of Example 1 was added to a four-functional alkoxysilane-modified resin ("E202C" manufactured by Arakawa Chemical Industries, (The above formula (10)) and epoxy equivalent 285) was changed to 1.8 parts by mass, a resin varnish was produced in exactly the same manner. Using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

&Lt; Comparative Example 3 &

1.8 parts by mass of a trifunctional alkoxysilane-modified resin (epoxy equivalent 285, E201, manufactured by Arakawa Chemical Industries, Ltd.) of Example 1 was mixed with 4 parts of a tetrafunctional alkoxysilane-modified resin ("P502" manufactured by Arakawa Chemical Industries, (11)) and 1.8 parts by mass of a phenolic hydroxyl group equivalent (300)), the resin varnish was prepared in exactly the same manner. Using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

&Lt; Comparative Example 4 &

100 parts by mass of spherical silica ("SOC2" manufactured by Admatex Co., Ltd., average particle size: 0.5 μm) of Example 1, 10 parts by mass of a trifunctional alkoxysilane-modified resin ("E201" manufactured by Arakawa Chemical Industries, 285) were directly added to the resin varnish in the same manner as in Production Example 1 except that the product 3 was added. Using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

&Lt; Comparative Example 5 &

100 parts by mass of spherical silica ("SOC2" manufactured by Admatex Co., Ltd., average particle size: 0.5 μm) of Example 1, 10 parts by mass of a trifunctional alkoxysilane-modified resin ("E201" manufactured by Arakawa Chemical Industries, 285) were directly added to the resin varnish in the same manner as in Production Example 1 except that the product 4 was added. Using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

&Lt; Comparative Example 6 >

, 1.8 parts by mass of a trifunctional alkoxysilane-modified resin ("E201" manufactured by Arakawa Chemical Industries, Ltd., epoxy equivalent 285) of Example 1 was mixed with an epoxy silane coupling agent (KBM403, Except that the weight of the resin varnish was changed to 100 parts by mass. Using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

The results are shown in Table 1.

From the results shown in Table 1, it can be seen that the resin compositions of Examples 1 to 5 have a low arithmetic mean roughness and a low root mean square roughness, and a sufficient value of the peel strength can be obtained. On the other hand, in Comparative Example 1, since the component (B) was not contained, the arithmetic average roughness and the square-root mean square roughness became large, and the peel strength also decreased. In Comparative Examples 2 to 6, the component (B) was not contained, and the arithmetic mean roughness and the root mean square roughness of the root mean square became larger, and the plating became swollen and the peel strength became remarkably small.

It is possible to provide a resin composition capable of forming a plated conductor layer having a small arithmetic average roughness and a square root mean square roughness of the surface of an insulating layer and a sufficient peel strength while maintaining the glass transition temperature and thermal expansion ratio It was. It is also possible to provide an adhesive film, a prepreg, a multilayer printed circuit board and a semiconductor device using the same. In addition, it is possible to provide vehicles such as computers, mobile phones, digital cameras, televisions and the like equipped with these, motorcycles, cars, tanks, ships, and aircraft.

Claims (12)

(A) an epoxy resin, (B) a trifunctional alkoxysilane-modified resin, and (C) an inorganic filler,
Wherein the epoxy resin comprises an epoxy resin which is liquid at a temperature of 20 캜 and an epoxy resin which is solid at a temperature of 20 캜 and whose mixing ratio (liquid epoxy resin: solid epoxy resin) is 1: 0.1 to 2 in mass ratio Composition. The resin composition according to claim 1, wherein part or all of the trifunctional alkoxysilane-modified resin (B) reacts with the inorganic filler (C) to form a reactant. The resin composition according to claim 2, which is obtained by reacting (B) a trifunctional alkoxysilane-modified resin with (C) an inorganic filler in advance, and then (A) adding to the epoxy resin. The resin composition according to any one of claims 1 to 3, wherein when the inorganic filler (C) is 100 parts by mass, the amount of the trifunctional alkoxysilane-modified resin (B) is 0.1 to 5 parts by mass. The epoxy resin composition according to any one of claims 1 to 3, wherein the trifunctional alkoxysilane-modified resin (B) is a trifunctional alkoxysilane-modified epoxy resin in which the hydroxyl group in the hydroxyl group- A trifunctional alkoxysilane-modified phenol resin in which the hydroxyl group is modified with silane, or both. The resin composition according to any one of claims 1 to 3, wherein the trifunctional alkoxysilane-modified resin (B) is represented by the following formula (1).

[In the formula (1), R ₃ is a linear or branched alkyl group having 1 to 10 carbon atoms or an allyl group, and each of R ₄ and R ₅ is independently hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms . In the formula (1), m represents 1 to 10. In the formula (1), X is selected from an epoxy resin or a phenol resin.] The resin composition according to any one of claims 1 to 3, wherein the trifunctional alkoxysilane-modified resin (B) is represented by the following formula (1).

[In the formula (1), R ₃ is a linear or branched alkyl group having 1 to 10 carbon atoms or an allyl group, and each of R ₄ and R ₅ is independently hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms . In the formula (1), m represents 1 to 10. In the formula (1), X is selected from a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a bisphenol S type epoxy resin and a novolak phenol resin. The method according to any one of claims 1 to 3, wherein the resin composition is cured to form an insulating layer, the surface of the insulating layer is roughened, and the peel strength between the conductor layer and the insulating layer obtained by plating is 0.43 kgf / cm 2 to 1.0 kgf / cm, the resin composition is cured to form an insulating layer, an arithmetic mean roughness after roughening the surface of the insulating layer is 10 nm to 300 nm, and a root mean square roughness is 10 nm to 520 nm By weight of the resin composition. An adhesive film in which the resin composition according to any one of claims 1 to 3 is laminated on a support. A prepreg impregnated with the resin composition according to any one of claims 1 to 3 in a sheet-like reinforcing base material. A multilayer printed wiring board in which an insulating layer is formed by a cured product of the resin composition according to any one of claims 1 to 3. A semiconductor device characterized by using the multilayered printed circuit board according to claim 11.