KR20140121783A - Curable resin composition - Google Patents

Abstract

The purpose of the present invention is to provide a curable resin composition, which has excellent elongation at break, and has the low root mean square roughness and low arithmetic mean roughness of the surface of the insulating layer in the wet conditioning process, and by which a plated conductive layer having sufficient peel strength can be formed, and which has a low coefficient of linear thermal expansion. A curable resin composition comprises (A) a phenoxy resin having an anthracene structure, (B) an epoxy resin, and (C) a curing agent, wherein in the case that the total of (A) the phenoxy resin, (B) the epoxy resin, and (C) the curing agent is 100 mass%, the phenoxy resin is 1-15 mass% and an epoxy equivalent of (A) the phenoxy resin is not less than 5000.

Description

CURABLE RESIN COMPOSITION [0001]

The present invention relates to a curable resin composition. The present invention also relates to a curable resin composition for an insulating layer, a sheet-like laminated material, a multilayer printed wiring board, and a semiconductor device containing the curable 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 are layered, and miniaturization and high density of wirings are required.

Various attempts have been made against this. For example, Patent Document 1 discloses that a polymer epoxy resin having a specific structure is used as a resin composition for a printed circuit board to improve heat resistance, low absorptivity, electrical characteristics, moldability, flexibility, impact resistance and adhesiveness (Claims and paragraph number 0003 etc.). However, Patent Document 1 discloses nothing about combining a phenoxy resin having an anthracene structure, an epoxy resin and a curing agent at a specific ratio, and using a phenoxy resin having a specific epoxy equivalent. In addition, Patent Document 2 discloses an epoxy resin having an anthracene structure. However, there are problems in that a phenoxy resin, an epoxy resin and a curing agent are combined at a specific ratio, and that a phenoxy resin having a specific epoxy equivalent is used, Is not disclosed.

Patent Document 1: JP-A-2003-252951 Patent Document 2: JP-A-2005-255813

A problem to be solved by the present invention is to provide a multilayer ceramic capacitor which has a specific strength (fracture elongation) and has an arithmetic average roughness lower than that of a surface of an insulating layer in a wet roughening process and has a root mean square (root mean square) (Low roughness), and a plating conductor layer having a sufficient fill strength can be formed, and the coefficient of linear thermal expansion is also low.

Means for Solving the Problem As a result of intensive studies to solve the above problems, the present inventors have found that a phenoxy resin having (A) an anthracene structure having a specific amount and a specific epoxy equivalent is contained together with (B) an epoxy resin and It has been found that the resin composition and the thermosetting resin thereof can achieve the above excellent strength, low lightness, high toughness and low coefficient of linear thermal expansion, and have completed the present invention.

That is, the present invention includes the following aspects.

[One]

A curable resin composition comprising (A) a phenoxy resin having an anthracene structure, (B) an epoxy resin, and (C) a curing agent, wherein the phenoxy resin (A), the epoxy resin (B) Wherein the phenoxy resin (A) is 1 to 15% by mass and the epoxy equivalent of the phenoxy resin (A) is 5000 or more when the total amount is 100% by mass.

[2]

The curable resin composition according to [1], wherein the weight average molecular weight of the phenoxy resin (A) is 8000 to 100000.

[3]

The curable resin composition according to [1] or [2], wherein the phenoxy resin (A) further has an unsubstituted or substituted biphenyl structure.

[4]

The epoxy resin composition according to any one of [1] to [3], wherein the epoxy resin (B) is at least one selected from the group consisting of bisphenol epoxy resin, crystalline bifunctional epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, A resin, and a mixture of these epoxy resins.

[5]

The curable resin composition according to any one of [1] to [4], wherein the curing agent (C) is selected from the group consisting of a phenol curing agent, a cyanate ester curing agent, an active ester curing agent and a mixture of these curing agents.

[6]

The curable resin composition according to [5], wherein the curing agent (C) is a cyanate ester curing agent or an active ester curing agent.

[7]

The curable resin composition according to any one of [1] to [6], wherein the content of the phenoxy resin (A) is 0.3 to 10% by mass, , The content of the epoxy resin is 5 to 30 mass%, and the content of the (C) curing agent is 3 to 20 mass%.

[8]

The curable resin composition according to any one of [1] to [7], further comprising (D) an inorganic filler.

[9]

The curable resin composition according to [8], wherein the inorganic filler (D) has an average particle diameter of 0.01 to 5 탆.

[10]

The content of the inorganic filler (D) in the curable resin composition of [8] or [9], when the nonvolatile component in the curable resin composition is 100% by mass, is 30 to 90% by mass.

[11]

The curable resin composition according to any one of [8] to [10], wherein the inorganic filler (D) is silica.

[12]

A curable resin composition for an insulating layer of a multilayered printed circuit board, which comprises the curable resin composition according to any one of [1] to [11].

[13]

A curable resin composition for a build-up layer of a multilayer printed circuit board, which comprises the curable resin composition according to any one of [1] to [11].

[14]

A sheet-like laminated material characterized by comprising the curable resin composition according to any one of [1] to [13].

[15]

A multilayer printed wiring board characterized by comprising an insulating layer obtained by thermally curing the curable resin composition according to any one of [1] to [13] or the sheet-laminated material according to [14].

[16]

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

Further, the present invention preferably includes the following cult.

[I] (A) a phenoxy resin having a weight average molecular weight of 25,000 to 40,000 and having an anthracene structure and a tetramethylbiphenyl structure,

(B) an epoxy resin selected from the group consisting of a bisphenol type epoxy resin, a crystalline bifunctional epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin and a mixture of these epoxy resins,

(C) a curing agent comprising at least one selected from a cyanate ester curing agent and an active ester curing agent, and

(D) an inorganic filler which is silica having an average particle diameter of 0.01 to 5 탆

, Wherein the curable resin composition

Wherein the phenoxy resin (A) is contained in an amount of 1 to 15% by mass based on 100% by mass of the total of the phenoxy resin (A), the epoxy resin (B), and the curing agent (C)

Wherein the epoxy equivalent of the phenoxy resin (A) is 9,000 to 15,000.

The insulating layer of the multilayered printed circuit board produced by thermosetting the curable resin composition of the present invention has excellent strength (fracture elongation), has an arithmetic average roughness lower than that of the surface of the insulating layer in the wet roughening process, It is possible to form a plated conductor layer having a low coefficient of linear expansion and a sufficient fill strength, and a coefficient of linear thermal expansion is also low.

Particularly, in the present invention, by using the phenoxy resin having the specific anthracene structure of the component (A), the above-mentioned low light intensity and high peak intensity can be achieved. In addition, the epoxy resin composition, which usually contains a relatively large amount of inorganic filler, has a problem that the resin flow in the thin film is lowered, voids are generated between the laminated conductors, and the peel strength tends to decrease. ) Can be used to improve the peel strength.

[Curable resin composition]

One embodiment of the present invention is a curable resin composition comprising (A) a phenoxy resin having an anthracene structure, (B) an epoxy resin, and (C) a curing agent, (A) the phenoxy resin is contained in an amount of 1 to 15% by mass and the epoxy equivalent of the phenoxy resin (A) is 5000 (A) when the total amount of the epoxy resin (B) and the curing agent Based on the total weight of the curable resin composition. Hereinafter, the curable resin composition of the present invention will be described in detail.

(A) a phenoxy resin having an anthracene structure

As the phenoxy resin having an anthracene structure usable in the present invention, any phenoxy resin can be used as long as it has an anthracene structure, for example, a phenoxy resin having at least one anthracene structure shown below.

Anthracene structure:

In Formula 1, R ₁ may be the same or different from each other may be, a group selected from the group consisting of a hydrocarbon group having a hydrogen atom, a halogen atom and a C _{1 ~ 10,} n is an integer from 0 to 8. Here, the halogen element may be fluorine, chlorine, bromine, iodine, or the like.

The phenoxy resin having an anthracene structure (A) is preferably a phenoxy resin having at least one anthracene structure and at least one structure other than an anthracene structure. Specifically, a phenoxy resin having a substituted or unsubstituted biphenyl structure and / or a bisphenol acetophenone structure is preferable. The substituted or unsubstituted biphenyl structure is shown below.

A substituted or unsubstituted biphenyl structure

In the formula 2, a group that is R ₂ and R ₃ may be the same if different from each other, selected from the group consisting of a hydrocarbon group having a hydrogen atom, a halogen atom and a C _{1 ~ 10,} m is an integer from 0 to 4. Here, the halogen element may be fluorine, chlorine, bromine, iodine, or the like.

Bisphenol acetophenone structure (see Japanese Patent Application Laid-Open No. 2003-252951)

(In Formula 3, R ₄ may be the phase may be equal to each other, a group selected from the group consisting of a hydrogen atom, a hydrocarbon group and a halogen atom C _{1 ~ 10,} R ₅ is a hydrocarbon group of a hydrogen atom, C _{1 ~ 10} a group selected from the group consisting of a group and a halogen atom, R ₆ is a hydrocarbon group a hydrogen atom or C _{1 ~ 10,} m is an integer from 0 to 5)

As a preferred embodiment, in Formula 1, R ₁ may be the or different from be the same with each other, a hydrocarbon group, a hydrogen atom or C _{1 ~ 8,} and more preferably a hydrogen atom or an alkyl group C _{1 ~ 6,} more preferably a hydrogen atom or Particularly preferably a hydrogen atom, and n may be the same or different and is an integer of 0 to 6, more preferably 0 to 4.

Preferred embodiment as in formula 2, R ₂ and R ₃ may be the phase may be equal to each other, and even hydrocarbon group a hydrogen atom or C _{1 ~ 8,} and more preferably a hydrogen atom or an alkyl group C _{1 ~ 6,} more preferably A hydrogen atom or a methyl group, particularly preferably a tetramethylbiphenyl structure, and m is an integer of 0 to 3, more preferably an integer of 1 to 2.

As a preferred embodiment, in Formula 3, R ₄ may be the phase may be equal to each other, a hydrocarbon group, a hydrogen atom or C _{1 ~ 8,} and more preferably a hydrogen atom or an alkyl group C _{1 ~ 6,} more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom, R ₅ is particularly a hydrogen atom or a methyl group, particularly preferably a hydrogen atom or an alkyl group C _{1 ~ 8} hydrocarbon group, preferably a hydrogen atom or a C _{1 ~ 6} than, more preferably is a hydrogen atom, R ₆ is a hydrogen atom or a C a hydrocarbon group of _{1 to 8,} more preferably a hydrogen atom or a C alkyl group of _{1 to 6,} more preferably is a hydrogen atom or a methyl group, and particularly preferably a methyl group, m Is an integer of 0 to 3, more preferably 1 to 2.

An example of a method for producing a phenoxy resin having an anthracene structure can be produced by reacting a hydroxy group of a dihydroxy anthracene derivative with an epoxy group of a substituted or unsubstituted biphenyl type epoxy resin. Specifically, the ratio of the number of epoxy groups of the substituted or unsubstituted biphenyl type epoxy resin to the number of hydroxyl groups of the dihydroxy anthracene derivative is preferably 1.5: 1 to 0.8: 1, more preferably 1.3: 1 to 0.9: 1 , More preferably from 1.1: 1 to 1: 1.

When the total amount of the phenoxy resin (A), the epoxy resin (B) described later and the curing agent (C) described later is 100 mass%, the content of the phenoxy resin having an anthracene structure (A) Is 1 to 15% by mass, preferably 2 to 13% by mass, and more preferably 5 to 10% by mass. When the content of the phenoxy resin is 1% by mass or more, a low arithmetic mean roughness and a low root mean square root roughness are obtained. When the content of the phenoxy resin is 15% by mass or less, And a low coefficient of linear thermal expansion can be maintained.

When the total amount of the phenoxy resin (A) and the epoxy resin (B) described later is 100 mass%, the amount of the phenoxy resin (A) is preferably 2 to 30 mass%, more preferably 4 to 4 mass% To 20% by mass.

The epoxy equivalent (mass of the resin containing one equivalent of epoxy group) of the phenoxy resin having an anthracene structure is, for example, 5000 (g / equivalent) or more, preferably 5,000 to 30,000 (G / equivalent), and more preferably 9000 to 15000 (g / equivalent), for example. When the phenoxy resin having an anthracene structure has an epoxy equivalent of 5000 or more, it has an excellent fracture elongation. When the epoxy equivalent is 30000 or less, the cross-linked site can be sufficiently retained, The coefficient can be maintained. The epoxy equivalent can be measured according to JIS K7236 (2001).

The weight average molecular weight of the phenoxy resin having an anthracene structure is, for example, 8000 to 100000, preferably 15000 to 80000, more preferably 20000 to 60000, and still more preferably 25000 to 40000. When the weight average molecular weight of the phenoxy resin is 8,000 or more, it has excellent breaking elongation. When the weight average molecular weight is 100000 or less, compatibility with the resin composition is improved, and low arithmetic average roughness and low root mean square roughness are possible. The weight average molecular weight of the phenoxy resin can be measured by gel permeation chromatography (GPC). Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene was measured using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K-804L can be calculated using a calibration curve of standard polystyrene at a column temperature of 40 ° C using chloroform or the like as the mobile phase.

When the nonvolatile component in the curable resin composition is 100 mass%, the content of the phenoxy resin (A) having an anthracene structure is preferably 0.3 to 10 mass%, more preferably 0.5 to 7 mass% And preferably 0.7 to 5% by mass.

(B) Epoxy resin

The epoxy resin as the component (B) is an epoxy resin different from the phenoxy resin as the component (A). The epoxy resin as the component (B) preferably has an epoxy equivalent different from that of the phenoxy resin as the component (A). (G / equivalent), more preferably 100 to 2000 (g / equivalent), and more preferably 100 to 2,000 (g / eq), of the epoxy equivalent of the epoxy resin Preferably 150 to 1000 (g / equivalent), particularly preferably 200 to 500 (g / equivalent). As a result, the crosslinking density of the insulating layer obtained from the curable resin composition becomes sufficient, and it becomes advantageous for lowering the luminance. The epoxy equivalent can be measured according to JIS K7236 (2001). Preferably, the epoxy resin is an epoxy resin having two or more epoxy groups in one molecule.

Specific examples of the epoxy resin of component (B) include bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and bisphenol AF type epoxy resin, dicyclopentadiene type epoxy Butadiene type epoxy resins, naphthalene type epoxy resins, naphthylene ether type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, epoxy resins such as phenol novolak type epoxy resins, A cresol novolak type epoxy resin, a biphenyl type epoxy resin, an anthracene type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spirocyclic epoxy resin, Dimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, crystalline 2 tube Epoxy resin or the like. More preferably, the epoxy resin (B) is a mixture of a bisphenol type epoxy resin, a crystalline bifunctional epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin and a mixture of these epoxy resins Group. These may be used singly or in combination of two or more.

Of these epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, crystalline bifunctional epoxy resins, dicyclopendadiene type epoxy resins, naphthalene type epoxy resins and mixtures of two or more thereof are preferable from the viewpoint of improvement in heat resistance Do. Specifically, for example, a mixture of bisphenol A type and F type mixed epoxy resin ("JX1059" manufactured by Shin-Nitetsu Kagaku Kogyo Co., Ltd.), bisphenol A type epoxy resin ("Epikote 828EL" manufactured by Mitsubishi Kagaku Kogyo Co., , "YL980", "jER1009"), bisphenol F type epoxy resin ("jER806H" and "YL983U" manufactured by Mitsubishi Kagaku K.K.), naphthalene type bifunctional epoxy resin ("HP-4032" (Trade name: HP-4032D, HP-4032SS, EXA4032SS), naphthalene type tetrafunctional epoxy resin (HP4700 and HP4710 manufactured by DIC Corporation), naphthol type epoxy resin Epoxy resin having a butadiene structure ("PB-3600", manufactured by Daicel Chemical Industries, Ltd., epoxy resin having a biphenyl structure "NC3000H" manufactured by Nihon Kayaku Co., Ltd., "ES- NC3000L ", " NC3100 "), YX4000H "," YX4000HK ", and" YL6121 "manufactured by Mitsubishi Chemical Corporation), an anthracene epoxy resin (" YX8800 "manufactured by Mitsubishi Kagaku Kagaku Co., Ltd., naphthylene EXA-7311 "," EXA-7311L ", and" EXA7311-G3 "manufactured by DIC Corporation), glycidyl ester type epoxy resin EX711 ", " EX721 ", " R540 ", manufactured by PRINTECO Corporation), and dicyclopentadiene type epoxy resin (HP-7200H manufactured by DIC Corporation).

The structural formula of the main component of HP4032SS is as follows.

The structural formula of YX4000HK is as follows.

(In the above formula, Gr is a glycidyl group)

The structural formula of HP-7200H is as follows.

(Wherein n is an integer of 1 to 20)

The structural formula of NC3000L is as follows.

(Wherein n is an integer of 1 to 20)

The content of the epoxy resin (B) is preferably 30 to 80% by mass, more preferably 30 to 70% by mass, more preferably 30 to 80% by mass when the total amount of the phenoxy resin (A) and the epoxy resin (B) By mass to 35% by mass to 75% by mass, and more preferably 40% by mass to 70% by mass.

The content of the epoxy resin (B) in the curable resin composition of the present invention is not particularly limited. However, from the viewpoint of achieving low illuminance and high peak strength of the insulating layer, the content of the nonvolatile component in the curable resin composition is preferably 100% , It is preferably from 5 to 30 mass%, more preferably from 7 to 25 mass%, and even more preferably from 10 to 20 mass%.

(C) Curing agent

The curing agent used in the present invention is not particularly limited as long as it is capable of crosslinking and curing the phenoxy resin and the epoxy resin. However, the curing agent is preferably a phenolic curing agent (phenol resin), a cyanate ester curing agent (cyanate ester resin) And a curing agent (active ester resin). These phenolic curing agents, cyanate ester curing agents and active ester curing agents can significantly lower the surface roughness of the insulating layer.

The phenol resin is not particularly limited, but biphenyl type phenol resin, naphthalene type phenol resin, phenol novolac resin, naphthylene ether type phenol resin and triazine skeleton containing phenol resin are preferable. Specifically, a biphenyl-type phenol resin MEH-7700, MEH-7810, MEH-7851 (manufactured by Meiwa Chemical Industries Ltd.), a naphthalene type phenol resin such as NHN, CBN, GPH (manufactured by Nippon Kayaku Co., SN-395 (manufactured by Shinnitetsu Kagaku Kabushiki Kaisha), EXB9500 (manufactured by DIC Corporation), SN-170, SN-180, SN-190, SN-475, SN-485, SN- LA-3018 and LA-7052 of a phenolic novolac resin, TD2090 (manufactured by DIC Corporation), naphthylene ether type phenolic resin EXB-6000 (manufactured by DIC Corporation) LA-7054, LA-1356 (manufactured by DIC Corporation), and the like. These may be used alone or in combination of two or more.

In addition, the structural formula of SN-485 is as shown below.

(In the formula (4), n is an integer of 1 to 20)

The structural formula of LA-7054 is shown in the following formula (5).

(In the above formula (5), n is an integer of 1 to 20)

The cyanate ester resin is not particularly limited, and examples thereof include novolak-type cyanate ester resins, dicyclopentadiene-type cyanate ester resins, bisphenol-type cyanate ester resins, and partially triarylated prepolymers thereof. Specifically, a phenol novolak type polyfunctional cyanate ester resin (PT30S, number average molecular weight: 380, PT60: number average molecular weight: 560, manufactured by Longji Japan K.K.) represented by the following formula (6), bisphenol A bisphenol A cyanate ester resin (BA230S75, manufactured by Longjana Japan K.K.), which is a prepolymer in which a part or all of the A type cyanate ester resin is triarized and trimerized, a dicyclopentadiene type Cyanate ester resin (DT-4000, DT-7000, manufactured by Longji Japan K.K.), and the like. Specifically, the number average molecular weight was measured using LC-9A / RID-6A manufactured by Shimadzu Corporation, Shodex KK, and Shodex K-800P / K-804L / K-804L manufactured by Showa Denko K.K. , Chloroform as the mobile phase, measurement at a column temperature of 40 占 폚, and calculation using a calibration curve of standard polystyrene. These may be used singly or in combination of two or more.

[In the above formula (6), n represents an arbitrary number (preferably 0 to 20, more preferably 1 to 10) as an average value.

(In the above formula (7), n represents an average value of 0 to 5)

The active ester resin usable in the present invention is a resin compound having at least one active ester group in one molecule. Here, the " active ester group " means an ester group which reacts with an epoxy resin. The active ester resin is preferably a resin compound capable of reacting with an epoxy resin and having two or more active ester groups in one molecule. Generally, a resin compound having two or more ester groups having a high reaction activity, which is selected from the group consisting of phenol esters, thiophenol esters, N-hydroxyamine esters and heterocyclic hydroxy compound esters in one molecule, Is preferably used. The active ester resin may be used alone or in combination of two or more.

From the viewpoint of improving heat resistance, an active ester resin obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound is more preferable. A phenol compound, a naphthol compound, and a thiol compound, and an active ester resin obtained by reacting the compound with a carboxylic acid compound are more preferable. An aromatic resin compound having two or more active ester groups per molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is even more preferable. An aromatic resin compound obtained by reacting a compound having at least two carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group and an aromatic resin having two or more active ester groups in one molecule of the aromatic resin compound Compounds are particularly preferred. The active ester resin may be straight-chain or multi-branched. In addition, if the compound having at least two carboxylic acids in one molecule contains a fat-chain, compatibility with the resin composition can be enhanced, and if the compound has an aromatic ring, the heat resistance can be increased.

Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferable from the viewpoint of heat resistance, and isophthalic acid and terephthalic acid are more preferable. Specific examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.

Specific examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- -Cresol, p-cresol, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6- dihydroxynaphthalene, dihydroxybenzophenone , Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadienyldiphenol, phenol novolac, and the like. Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydro Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclo Pentadienyldiphenol and phenol novolak are preferable, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydro More preferred are phenoxy novolac, 1,5-dihydroxynaphthalene, 1,6-dihydroxy naphthalene, 1,6-dihydroxybenzophenone, Naphthalene, 2,6-dihydroxyl More preferred are naphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol and phenol novolak, and 1,5-dihydroxy naphthalene, 1,6-dihydro Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyldiphenol and phenol novolac are more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6- Dihydroxynaphthalene, dicyclopentadienyl diphenol is particularly preferred, and dicyclopentadienyl diphenol is particularly preferred. Specific examples of the thiol compound include benzenedithiol, triazinedithiol, and the like.

Specific examples of the active ester resin include an active ester resin containing a dicyclopentadienyldiphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylated phenol novolac, a benzoylphenol novolak Among them, an active ester resin having a naphthalene structure and an active ester resin having a dicyclopentadienyldiphenol structure are more preferable. As commercial products, EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC Corporation) as an active ester resin containing a dicyclopentadienyldiphenol structure, EXB9416-70BK as an active ester resin containing a naphthalene structure (Manufactured by DIC Corporation), DC 808 (manufactured by Mitsubishi Chemical Corp.) as the active ester resin containing acetylated phenol novolak, YLH1026 (manufactured by Mitsubishi Chemical Corporation) as an active ester resin containing benzoylated phenol novolac Ltd.), and the like.

Particularly preferred active ester resins are represented by the following formula (9)

(In the above formula (9), m is 0 or 1, and n is an average value of 0.25 to 1.5, and preferably 0.4 to 1.2), and X-group and XO - group (wherein X is a phenyl group or a naphthyl group which may have a substituent)

Respectively. The weight average molecular weight of the active ester resin is preferably 1,500 to 4,000, more preferably 2,000 to 3,000.

Particularly preferred active ester resins each have a dicyclopentadienyldiphenol structure represented by the following formula (10), and each has an X- group and an XO- group (wherein X is a naphthyl group which may have a substituent) , HPC-8000-65T which is an active ester resin having a weight average molecular weight of about 2700.

(In the above formula (10), m is 0 or 1, and n is an average value of 0.4 to 1.2)

The content of the curing agent (C) in the curable resin composition of the present invention is not particularly limited, but from the viewpoint of lowering the insulating layer and achieving high peak strength, when the nonvolatile component in the curable resin composition is 100% by mass , Preferably 3 to 20 mass%, more preferably 5 to 18 mass%, and still more preferably 7 to 15 mass%.

When the total number of epoxy groups in the epoxy resin is 1, the number of reactors of the curing agent is preferably 0.2 to 2, more preferably 0.3 to 1.5, still more preferably 0.4 to 1. Here, the "number of epoxy groups in the whole epoxy resin" is a value obtained by dividing the value obtained by dividing the solid content of each epoxy resin present in the curable resin composition by the epoxy equivalent, relative to the total epoxy resin. The term " reactor " means a functional group capable of reacting with an epoxy group, and the term " reactor number " is a total value obtained by dividing the solid content of the curing agent present in the resin composition by the reactor equivalent.

(D) inorganic filler

Examples of the inorganic filler usable in the present invention include silica, alumina, mica, mica, silicic salt, barium sulfate, magnesium hydroxide and titanium oxide. Silica and alumina are preferable. Amorphous silica, Silica such as fused silica, crystalline silica, synthetic silica, hollow silica and spherical silica is preferable, and spherical silica and fused silica are more preferable. From the viewpoint of improving the filling property of the inorganic filler to the sheet-like laminate material of the present invention including the curable resin composition, spherical fused silica is more preferable. One or more inorganic fillers may be used. As commercially available spherical fused silica, "SOC2" and "SOC1" manufactured by Adomex Co., Ltd. may be mentioned.

The average particle diameter of the inorganic filler is not particularly limited, but is preferably 5 占 퐉 or less, more preferably 3 占 퐉 or less, further preferably 1 占 퐉 or less, and most preferably 0.8 占 퐉 or less, from the viewpoint of forming fine wiring on the insulating layer. Mu m or less, and particularly preferably 0.6 mu m or less. On the other hand, when the curable resin composition is a varnish, from the viewpoint of increasing the viscosity of the varnish and preventing the handling property from being lowered, it is preferably 0.01 탆 or more, more preferably 0.03 탆 or more, More preferably 0.1 mu m or more. 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 scattering particle size distribution measuring apparatus, and the median diameter of the inorganic filler is determined as the average particle diameter. The measurement sample can be preferably those in which an inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, LA-500 manufactured by Horiba Seisakusho Co., Ltd. or the like can be used.

Although the content of the inorganic filler is not particularly limited, from the viewpoint of preventing the flexibility of the sheet form of the sheet-like laminated material from being lowered, when the amount of the inorganic filler is 30 By mass to 90% by mass, more preferably 40% by mass to 85% by mass, still more preferably 50% by mass to 85% by mass. Particularly in the present invention, it is possible to improve the peel strength even in a curable resin composition containing 50 mass% or more of an inorganic filler.

The inorganic filler is preferably surface-treated (coated) with a coupling agent or the like in order to improve the heat resistance and the dispersibility. As the surface treating agent (coupling agent), at least one selected from an epoxy silane coupling agent, an aminosilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, and a titanate coupling agent desirable. Among these, the aminosilane-based coupling agent is preferable because it is excellent in moisture resistance, dispersibility, and cured properties, and is more preferably a phenylaminosilane-based coupling agent. As commercially available products, KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM803 (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., KBE903 "(3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.," KBM573 "(N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., KBM103 " (phenyltrimethoxysilane) manufactured by Kakugo Kogyo K.K., and SZ-31 (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and the like.

[Other components]

In the curable resin composition of the present invention, besides the above-mentioned components, other components such as a curing accelerator; Thermoplastic resin; Thermosetting resins such as vinyl benzyl compounds, acrylic compounds, maleimide compounds, and block isocyanate compounds; Flame retardants such as phosphorus compounds and metal hydroxide; Organic fillers such as silicone powder, nylon powder, fluorine powder, and rubber particles; Organic solvent; Thickeners such as oven, bentone and the like; Silicone-based, fluorine-based, and high-molecular antifoaming agents; Adhesion-imparting agents such as imidazole-based, thiazole-based, triazole-based and silane coupling agents; Colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow and carbon black; Additives and the like can be appropriately added.

As the curing accelerator, any curing accelerator may be used as long as it can accelerate the crosslinking and curing of the epoxy resin by the curing agent. For example, an amine compound, a guanidine compound, an imidazole compound, a phosphonium compound and a metal curing accelerator And the like. These may be used singly or in combination of two or more.

Examples of the compound usable in the present invention include, but are not limited to, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris Dimethylaminomethyl) phenol, and amine compounds such as 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU). These may be used singly or in combination of two or more. These may be used singly or in combination of two or more.

As the imidazole compound which can be used in the present invention,

(In Formula 11, R ₇ to R ₁₀ is a cyano group, a nitro group, formyl group, C _{1 ~ 20} alkyl group be a hydrogen atom, a halogen atom, a, may be different even if the same, respectively, C _{2 ~ 20} alkenyl group, C _{2 ~ 20} alkynyl group, C _{3 ~ 20} allyl group, C _{4 ~ 20} alkyl diethoxy group, C _{4 ~ 20} group to the poly, C _{6 ~ 20} aryl group, C _{6 ~ 20} alkylaryl group, C _{6 ~ 20} aryl group, C _4-20 cycloalkyl group, C _4-20 cycloalkyl alkenyl, (C _{5 ~ 10} cycloalkyl) C _1-10 alkyl, C good silyl group which may have a group _{1 to 10} hydrocarbon group, a hydroxy group derived from an epoxy resin)

May be used.

More specifically, the imidazole compound is selected from the group consisting of 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl- (1 ') -] - < / RTI > 2-methylimidazolyl- Ethyl-S-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')] (1 ')] - ethyl-S-triazine, 2,4-diamino-6- [2'-methylimidazolyl- 2-phenyl-4-methyl-5-methyl-imidazole, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, Phenylmethylimidazole, 2-phenyl-4-methylimidazole, an adduct of an imidazole compound and an epoxy resin, and 2,4-diamino-6-vinyl-S-triazine ≪ / RTI > These may be used singly or in combination of two or more.

The metal-based curing accelerator which can be used in the present invention 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 (Co (II) Ac) and cobalt (III) acetylacetonate (Co (III) Ac), copper (II) acetylacetonate An organic copper complex of zinc (II), an organic zinc complex such as zinc (II) acetylacetonate, an organic iron complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, And organic manganese complexes such as nate. Examples of the organometallic 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.

The content of the curing accelerator is preferably in the range of 0.005 to 3 mass%, more preferably in the range of 0.01 to 1 mass%, in the case where the total amount of the nonvolatile component in the curable resin composition is 100 mass% Do.

As the thermoplastic resin, for example, (A) a phenoxy resin other than a phenoxy resin having an anthracene structure, a polyvinyl acetal resin, a polyimide resin, a polyamideimide resin, a poly Ether sulfone resin, cycloolefin polymer, and polysulfone resin, and polyvinyl acetal resin is preferable. These may be used singly or in combination of two or more.

The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8000 to 70000, more preferably in the range of 10000 to 60000, and further preferably in the range of 20,000 to 60,000. The weight average molecular weight of the thermoplastic resin in terms of polystyrene can be measured by a gel permeation chromatography (GPC) method in the same manner as in (A) measuring the weight average molecular weight of the phenoxy resin.

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, N-dimethylacetamide, N-methylpyrrolidone, and the like, and the like can be given as examples of the aromatic hydrocarbon solvent. Two or more kinds of organic solvents may be used in combination.

[Preparation of curable resin composition]

The curable resin composition of the present invention may be prepared by appropriately mixing the above components and further mixing them with a kneading means such as a three roll, a ball mill, a bead mill or a sand mill or a high speed rotary mixer, a super mixer, a planetary mixer By means of an agitating means such as a kneader or the like. Further, it can be prepared as a resin varnish by adding the above-mentioned organic solvent.

In the curable resin composition of the present invention, a plating conductor layer having not only a low arithmetic mean roughness on the surface of the insulating layer but also a low root mean square roughness and a sufficient fill strength can be formed. In the production of a multilayer printed wiring board, Can be suitably used as a curable resin composition for an insulating layer of a multilayer printed wiring board. Further, it can be suitably used as a curable resin composition for forming a conductor layer by plating (a resin composition for an insulating layer of a multilayered printed circuit board on which a conductor layer is formed by plating), and furthermore, a curable resin composition for a build- .

The form of the curable resin composition of the present invention is not particularly limited, but it can be applied to a sheet-like laminated material such as an adhesive film and a prepreg, a circuit board (laminated board use, use of a multilayer printed wiring board, and the like). The curable 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 laminated material such as an adhesive film or a prepreg . The softening point of the curable resin composition is preferably 40 to 150 DEG C from the viewpoint of the lamination property of the sheet-like laminated material.

[Multilayer Printed Circuit Board]

The curable resin composition of the present invention can be used as a curable composition for an insulating layer of a multilayered printed circuit board. The multilayer printed wiring board that can be used in the present invention is a multilayer printed wiring board including an insulating layer obtained by thermally curing the curable resin composition or sheet-laminated material of the present invention.

Here, the conditions of the thermosetting may be appropriately selected according to the kind, the content, and the like of the epoxy resin in the curable resin composition. For example, the curing temperature is 90 to 220 占 폚, preferably 160 to 210 占 폚, 10 minutes to 180 minutes, preferably 20 to 120 minutes. In addition, thermal curing may be performed in two steps.

The coefficient of linear thermal expansion (CTE) (JIS K7197) of the insulating layer is preferably 20 ppm / ° C or less, more preferably 19 ppm / ° C or less, as measured by an average coefficient of linear thermal expansion of 25 to 150 ° C Do. The lower limit value is not particularly limited, but is generally 4 ppm / ° C. Thus, deformation of the insulating layer (buildup layer) and the conductor layer (wiring) can be prevented, and a highly reliable multilayer printed wiring board can be obtained.

The surface of the insulating layer may be roughened. As the harmonic treatment of the dry type, plasma treatment and the like can be given. The harmonization of the wet process is performed, for example, by applying various process liquids. A swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid are carried out in this order. Therefore, the treatment liquid may be a kit of these swelling liquid, oxidizing agent, and neutralizing liquid. The wet roughening treatment is preferable in view of high productivity because a large area or a plurality of sheets can be processed at one time.

The swelling treatment with the swollen liquid is carried out by immersing the insulating layer in the swollen liquid at 50 to 80 DEG C for 5 to 20 minutes (preferably at 55 to 70 DEG C for 8 to 15 minutes). The swelling liquid includes, for example, an alkali solution, a surfactant solution and the like, preferably an alkali solution. Examples of the alkali solution include a sodium hydroxide solution, a potassium hydroxide solution and the like. Examples of commercially available swelling liquids include Swelling Dip Securiganth P and Swelling Dip Securgiganth SBU manufactured by Atotech Japan KK.

The coarsening treatment with an oxidizing agent is carried out by immersing the insulating layer in an oxidizing agent solution at 60 to 80 占 폚 for 10 to 30 minutes (preferably at 70 to 80 占 폚 for 15 to 25 minutes). As the oxidizing agent, for example, 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 can be given. The concentration of permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP manufactured by Atotech Japan Ltd., and Dozing Solution Seq.

The neutralization treatment by the neutralization liquid is carried out by immersing the neutralization liquid at 30 to 50 DEG C for 3 to 10 minutes (preferably 35 to 45 DEG C for 3 to 8 minutes). As the neutralizing solution, an acidic aqueous solution is preferable, and commercially available products include, for example, Reduction Solution · Securigans P manufactured by Atotech Japan K.K.

After the roughening treatment, the insulating layer may be dried at 50 to 120 DEG C for 10 to 60 minutes (preferably at 60 to 100 DEG C for 20 to 40 minutes).

The surface roughness of the surface of the insulating layer after the roughening treatment preferably has an arithmetic mean roughness (Ra) of 350 nm or less, more preferably 300 nm or less, further preferably 250 nm or less , And particularly preferably 100 nm or less. The lower limit value of the arithmetic mean roughness (Ra) is not limited, but is generally 10 nm or more, 40 nm or more, 70 nm or more, and the like. The root mean square roughness (Rq) is preferably not more than 500 nm, more preferably not more than 450 nm, even more preferably not more than 350 nm, and particularly preferably not more than 150 nm. The lower limit value of the root mean square root roughness (Rq) is not limited, but generally 20 nm or more, 50 nm or more, 90 nm or more. In addition, since the local average roughness Rq of the root mean square roughness reflects the local state of the surface of the insulating layer, it can be confirmed that the surface of the insulating layer becomes more dense and smooth by grasping Rq, and the peak strength is stabilized. This corresponds to the surface roughness of the insulating layer after the curing resin composition is thermally cured and subjected to the roughening treatment.

The fill strength is preferably greater than or equal to 0.45 kgf / cm (4.41 N / cm) and more preferably greater than or equal to 0.50 kgf / cm (4.90 N / cm) to provide sufficient adhesion between the insulating layer and adjacent layers, More preferable. (14.7 N / cm) or less, 1.2 kgf / cm (11.8 N / cm) or less and 1.0 kgf / cm (9.81 N / cm) in general, though there is no particular limitation, Or less, or 0.8 kgf / cm (7.85 N / cm) or less.

The tensile strength of the cured product obtained by thermosetting the curable resin composition is measured according to JIS K7127. Specifically, a test piece cut out from the cured product into a dumbbell can be prepared, and the PET film can be peeled off and measured using a tensile tester RTC-1250A manufactured by Olentech. The elongation at break is preferably 1.5% or more, more preferably 1.6% or more, and further preferably 1.7% or more.

[Sheet-like laminated material]

The sheet-like laminate material used in the present invention is a sheet-like material before curing, in which the above-mentioned curable resin composition is layered. The sheet-like laminated material can be prepared by a method known to a person skilled in the art, for example, by preparing a resin varnish obtained by dissolving a resin composition in the organic solvent described above, applying the resin varnish to a support using a die coater or the like, , Or by drying the organic solvent by heating with hot air or by blowing hot air to form a resin composition layer (sheet-laminated material) on a support, as a sheet-like laminate material with a support. The sheet-like laminated material may also be used as a prepreg by impregnating the resin varnish with a sheet-like reinforcing base material such as glass cloth by a hot-melt method or a solvent method. Further, the sheet-like laminated material with a support may be referred to as an adhesive film.

The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. The amount of the organic solvent in the varnish and the boiling point of the organic solvent, but the varnish containing, for example, 30 to 60 mass% of the organic solvent is dried at 50 to 150 캜 for about 3 to 10 minutes to form the resin composition layer .

The thickness of the obtained sheet-like laminated material is not particularly limited, but is preferably in the range of, for example, 1 to 150 탆, more preferably in the range of 2 to 100 탆, further preferably in the range of 3 to 50 탆, And particularly preferably in the range of 5 to 30 mu m.

The sheet-like laminate material may have a plurality of resin composition layers, a support on one side of the resin composition layer, and a protective film on the other side.

[Support]

Examples of the support which can be used in the present invention include a plastic film and a metal foil. Specific examples of the plastic film include polyethylene terephthalate (hereinafter may be abbreviated as "PET"), polyester such as polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, acrylic, cyclic polyolefin, triacetylcellulose, polyether sulfide , Polyether ketone, polyimide, and the like. Among them, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable, and a polyethylene terephthalate film which is particularly inexpensive and easy to obtain is preferable.

Examples of the metal foil include copper foil and aluminum foil.

In view of versatility, a plastic film is preferable, and in the case of using a plastic film, it is preferable to use a support on which a surface contacting with a layer containing a curable resin composition has been subjected to a release treatment, in order to improve peelability. The releasing agent used in the releasing treatment is not particularly limited as long as the layer containing the curable resin composition can be peeled from the support layer, and examples thereof include a silicone releasing agent, an alkyd resin releasing agent, a polyolefin resin, a urethane resin, have. As the support subjected to the releasing treatment, a commercially available plastic film with a release layer may be used. Preferred examples thereof include PET films SK-1 and AL-5 having a release layer composed mainly of an alkyd resin- , And AL-7 (manufactured by LINTEC K.K.). The plastic film may be subjected to a mat treatment or a corona treatment, or a release layer may be formed on the treated surface. On the other hand, the metal foil may be removed by an etching solution, or the metal foil may be used as a conductor layer without being removed.

The thickness of the support is not particularly limited, but is preferably in the range of 10 to 150 mu m, more preferably in the range of 20 to 50 mu m, and further preferably in the range of 25 to 45 mu m.

The protective film usable in the present invention may be formed for the purpose of preventing adhesion of dust or the like to the layer containing the curable resin composition. As the protective film, the same plastic film as the support may be used. The protective film may be subjected to a surface treatment such as a mat treatment or a corona treatment, or may be subjected to the same releasing treatment as described above. The thickness of the protective film is preferably 3 to 30 mu m, more preferably 5 to 20 mu m.

[Multilayered printed wiring board using sheet-like laminated material]

Next, an example of a method for manufacturing a multilayer printed wiring board using the sheet-laminated material produced as described above will be described.

First, the sheet-like laminated material is laminated (laminated) on one side or both sides of a circuit board using a vacuum laminator. As the substrate used for the circuit board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate and the like can be given. Here, the circuit board refers to 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 outermost layer of the multilayered printed circuit board is also formed as a conductor layer (circuit) patterned on both sides or both sides. do. Further, the surface of the conductor layer may be previously subjected to a roughening treatment by blackening treatment, copper etching, or the like.

If the sheet-like laminate material has a protective film in the laminate, the protective film is removed, and if necessary, the sheet-like laminate material and the circuit board are preheated, and the laminate material is pressed and heated on the circuit board Laminate. In the sheet-like laminated material of the present invention, a method of laminating a circuit board under reduced pressure by a vacuum lamination method is suitably used. The lamination conditions are not particularly limited. For example, the laminate is reduced in pressure by about 20 mmHg (26.7 hPa) or less for about 10 to 120 seconds, and then the compression temperature (laminate temperature) is preferably 70 to 140 DEG C, The lamination pressure is preferably 0.1 to 1.5 MPa, more preferably 0.5 to 1.2 MPa, and the pressing time (lamination time) is preferably 5 to 180 seconds. The lamination method may be a batch method or a continuous method in a roll. Vacuum laminates can be made using commercially available vacuum laminators. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nichigo & Motton Kabushiki Kaisha, a vacuum pressurized laminator manufactured by Takeda Chemical Industries, Ltd., a roll-type dry coater manufactured by Hitachi Industries, Ltd., Hitachi AIC And a vacuum laminator manufactured by Kao Corporation.

Thereafter, when the support is peeled off after cooling to about room temperature (25 캜), the insulating layer can be formed on the circuit board by peeling off and thermally curing the resin composition to form a cured product. For example, the curing temperature is 100 to 220 占 폚, preferably 160 to 210 占 폚, and the curing time is 20 to 180 占 폚. Min, preferably 30 to 120 minutes. In addition, thermal curing may be performed in two steps. If the support is not peeled off after the formation of the insulating layer before curing, peeling may be performed here if necessary.

The sheet-like laminated material may also be laminated on one side or both sides of the circuit board using a vacuum press. The lamination step of applying pressure and heating under reduced pressure can be carried out using a general vacuum hot press machine. For example, a metal plate such as a heated SUS plate can be pressed from the support side. The pressing conditions are that the pressure is reduced under a pressure of usually 0.01 MPa or less, preferably 0.001 MPa or less, at a temperature of 70 to 250 캜, preferably 100 to 230 캜, a pressing pressure is in a range of 0.5 to 4 MPa, For 30 to 150 minutes. The heating and pressurization can be carried out in one step, but it is preferable to carry out the heating and pressurization in two or more stages from the viewpoint of controlling the flowing out of the resin. For example, it is preferable to perform the first-stage press at a temperature of 70 to 150 ° C, a press pressure of 0.1 to 1.5 MPa, a second-stage press at a temperature of 150 to 200 ° C, and a pressure of 0.5 to 4 MPa. The time for each step is preferably 20 to 120 minutes. By thermally curing the resin composition layer in this manner, the insulating layer can be formed on the circuit board. Examples of commercially available vacuum hot presses include MNPC-V-750-5-200 (manufactured by Meikisha Sakusho Co., Ltd.) and VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.).

Then, a via hole and a through hole may be formed by perforating the insulating layer formed on the circuit board. The drilling can be carried out by a known method such as drilling, laser, plasma or the like, and also by combining these methods as required. The drilling using a laser such as a carbon dioxide gas laser or a YAG laser is most effective This is a common method. In the case where the support is not peeled off before the drilling, the peeling is carried out here.

Then, the above-mentioned roughening treatment is carried out on the surface of the insulating layer, and the conductive layer can be further 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. Examples of the wet plating include a method of forming a conductor layer by combining electroless plating and electrolytic plating, a method of forming a plating resist having a pattern reverse to that of the conductor layer, and forming a conductor layer by electroless plating only. As a method of forming the pattern thereafter, for example, a subtractive method and a semi-known method known to those skilled in the art can be used. By repeating the above-described series of steps a plurality of times, a multi- And becomes a printed wiring board. In the present invention, since it is low in shade and high in fill, it can be suitably used as a build-up layer of a multilayer printed wiring board.

[Semiconductor device]

A semiconductor device can be manufactured by using the multilayer printed wiring board manufactured as described above. A semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of a multilayered printed circuit board that can be used in the present invention. The " conduction portion " is a " portion for transmitting an electrical signal in the multilayered printed circuit board ", and may be a surface or a buried portion. Further, it may be a part of the conductor layer as long as it conducts, or may be a conductive part such as other connectors. 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 in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip effectively functions. Specifically, the semiconductor chip is manufactured by a wire bonding method, a flip chip mounting method, A mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like.

[Example]

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples. In the following description, "part" means "part by mass" unless otherwise specified, and "%" means "% by mass" unless otherwise specified.

<Methods of measurement and evaluation>

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

[Preparation of Samples for Measurement of Peel Strength, Arithmetic Mean Roughness (Ra Value), Peak Mean Square Root Roughness (Rq Value)]

(1) Underlining of laminates

Both surfaces of a copper clad epoxy resin double-sided copper clad laminate (copper foil thickness 18 占 퐉, substrate thickness 0.3 mm, R5715ES manufactured by Matsushita Electric Industrial Co., Ltd.) were subjected to 1 占 퐉 etching with CZ8100 manufactured by McGraw- Respectively.

(2) Laminate of adhesive film

The adhesive films prepared in Examples and Comparative Examples were laminated on both sides of the epoxy resin double-sided copper clad laminate subjected to the roughening treatment by using a batch vacuum laminator MVLP-500 (manufactured by Meikisha Sakusho). The laminate was subjected to pressure reduction for 30 seconds to set the air pressure to 13 hPa or less, and then to press for 30 seconds at 100 占 폚 under a pressure of 0.74 MPa.

(3) Curing of resin composition

After the polyethylene terephthalate (PET) film as a support was peeled off from the laminated adhesive film, the resin composition was cured at 100 占 폚 for 30 minutes and then at 180 占 폚 for 30 minutes to form an insulating layer.

(4) Harmonization processing

The laminate having the insulating layer formed thereon was immersed in a swelling dip dip sealer P (glycol ethers and aqueous solution of sodium hydroxide) containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd., which is a swelling liquid, at 60 占 폚 And immersed for 5 minutes (Example 1, Comparative Examples 1, 4 and 5) or 10 minutes (Examples 2 and 3, Comparative Examples 2 and 3). Next, as a roughening solution, a solution of concentrate P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) of Atotech Japan Co., Ltd. for 15 minutes (Example 1, 4, and 5) for 20 minutes (Examples 2 and 3, Comparative Examples 2 and 3). Finally, as a neutralizing solution, it was immersed in a Reduction Solution ㆍ Securigans P (aqueous solution of sulfuric acid) of Atotech Japan Co., Ltd. at 40 ° C for 5 minutes. After drying at 80 DEG C for 30 minutes, this substrate was referred to as evaluation substrate A.

(5) Plating by semi-specific method

Evaluation board A was plated to form a conductor layer. Specifically, the evaluation substrate A was immersed in a solution for electroless plating containing PdCl ₂ at 40 ° C for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C for 20 minutes. After an annealing process was performed by heating at 150 占 폚 for 30 minutes, an etching resist was formed, a pattern was formed by etching, and copper sulfate electroplating was performed to form a conductor layer with a thickness of 30 占 퐉. Next, annealing was performed at 190 캜 for 60 minutes. This substrate was referred to as evaluation substrate B.

[Measurement of arithmetic mean roughness (Ra value), root mean square root roughness (Rq value) after harmonization]

The evaluation substrate A was evaluated by using a non-contact surface roughing machine (WYKO NT3300 manufactured by Vico Instruments Inc.), and the value obtained by setting the measurement range to 121 占 퐉 92 占 퐉 by the VSI contact mode, , And Rq values were obtained. And the average value of 10 points was obtained.

[Measurement of Peel Strength (Peel Strength) of Plated Conductor Layer)

A section of a width of 10 mm and a length of 100 mm was inserted into the conductor layer of the evaluation board B and held with a tool (TSE, autocompact type tester AC-50C-SL) for detaching and holding the one end, (Kgf / cm (N / cm)) when 35 mm was removed in the vertical direction at a speed of 50 mm / minute.

[Measurement of linear thermal expansion coefficient (CTE)]

The adhesive films obtained in Examples and Comparative Examples were thermally cured by heating at 200 DEG C for 90 minutes and a PET film as a support was peeled off to obtain a cured product on a sheet. The cured product was cut into test pieces having a width of 5 mm, a length of 15 mm and a thickness of 30 mm, and thermomechanical analysis was carried out by a 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 linear thermal expansion (ppm) from 25 占 폚 to 150 占 폚 in the second measurement was calculated.

[Measurement of fracture elongation]

The adhesive films obtained in Examples and Comparative Examples were thermally cured by heating at 200 DEG C for 90 minutes, and the cured product was cut into dumbbells and the PET film was peeled off to obtain test pieces. The test piece was subjected to tensile strength measurement using a tensile tester RT-C-1250A manufactured by Orientech, in accordance with JIS K7127, and the fracture elongation at 23 占 폚 was determined.

&Lt; Synthesis Example 1 &

Synthesis of phenoxy resin having an anthracene structure and tetramethylbiphenyl structure

191 g of tetramethylbiphenyl type epoxy resin (YX4000, manufactured by Mitsubishi Kagaku KK, epoxy equivalent 185), 210 g of 9,10-dihydroxyanthracene (phenolic hydroxyl equivalent 210) and 150 g of cyclohexanone were placed in a reaction container And dissolved by stirring. Subsequently, 0.5 g of tetramethylammonium chloride solution was added dropwise, and the mixture was reacted at 180 占 폚 for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was filtered using a filter cloth and diluted with a solvent to obtain a phenoxy resin A.

· Epoxy equivalent: 11000

Weight average molecular weight: 35000

A 1: 1 solution of MEK with a solids content of 30% by mass and cyclohexanone

The phenoxy resin A had the following structure.

&Lt; Synthesis Example 2 &

Synthesis of phenoxy resin having tetramethylbiphenyl structure and bisphenolacetophenone structure

100 g of tetramethylbiphenyl-type epoxy resin ("YX4000" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), 80 g of bisphenol acetophenone (phenolic hydroxyl equivalent 145) and 150 g of cyclohexanone were placed in a reaction vessel and stirred . Subsequently, 0.5 g of tetramethylammonium chloride solution was added dropwise, and the mixture was reacted at 180 占 폚 for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was filtered using a filter cloth and diluted with a solvent to obtain a phenoxy resin B. The phenoxy resin B does not have an anthracene structure and is therefore a reference example of the present invention.

· Epoxy equivalent: 13000

Weight average molecular weight: 38000

A 1: 1 solution of MEK having a solid content of 30% by mass and cyclohexanone was prepared.

The phenoxy resin B had the following structure.

 &Lt; Example 1 >

, 10 parts of a bisphenol-type epoxy resin ("ZX1059" manufactured by Shin-Etsu Chemical Co., Ltd., a 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 10 parts of a crystalline bifunctional epoxy resin (manufactured by Mitsubishi Chemical Corporation , 10 parts of epoxy resin ("YX4000HK" manufactured by Mitsui Chemicals, Inc., epoxy equivalent: about 185) and 20 parts of dicyclopentadiene type epoxy resin ("HP-7200H" manufactured by DIC Corporation, epoxy equivalent: 275) were dissolved by heating in 35 parts of solvent naphtha . After cooling to room temperature (25 캜), 12 parts of phenoxy resin A, 12 parts of phenol-based curing agent containing triazine skeleton ("LA-7054" manufactured by DIC Corporation, hydroxyl group equivalent 125, , 15 parts of a naphthalene type curing agent ("SN-485" manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl group equivalent 215, solid content 60%, MEK solution), 15 parts of a curing accelerator (4-dimethylaminopyridine 10 parts by weight of a flame retardant ("HCA-HQ" manufactured by Sankyo Kabushiki Kaisha, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene- (Average particle diameter: 2 탆), 2 parts of spherical silica surface-treated with phenylamino silane coupling agent (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle diameter: 0.24 탆, manufactured by Adomex Co., Quot ;, and a carbon content per unit area of 0.36 mg / m &lt; 2 &gt;) were uniformly dispersed in a high-speed rotary mixer , And a resin varnish was produced. Subsequently, a resin varnish was uniformly applied on the release surface of a polyethylene terephthalate film with a release treatment ("AL5" manufactured by LINTEC CORPORATION, thickness 38 μm) so that the thickness of the resin composition layer after drying was 30 μm, And dried at 120 캜 (average 100 캜) for 4 minutes to produce an adhesive film.

&Lt; Example 2 >

, 5 parts of liquid naphthalene type epoxy resin (epoxy equivalent 144, "HP4032SS" manufactured by DIC Corporation), 5 parts of crystalline bifunctional epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 185) 12 parts of epoxy resin ("NC3000L" manufactured by Nihon Kayaku Co., Ltd., epoxy equivalent 269) was dissolved by heating in 30 parts of solvent naphtha with stirring. After cooling to room temperature (25 캜), 5 parts of phenoxy resin A, 5 parts of bisphenol A dicyanate prepolymer ("BA230S75" manufactured by Longji Japan Co., Ltd., cyanate equivalent approximately 232, 75% , 6 parts of a phenol novolac-type polyfunctional cyanate ester resin ("PT30S" manufactured by Longji Japan K.K., a cyanate equivalent weight of about 133, a non-volatile matter content of 85% by mass, MEK solution), 20 parts of a curing accelerator 1 part by mass of a solid content of MEK solution), 1 part of a curing accelerator (cobalt (III) acetylacetonate (Co (III) Ac) manufactured by Tokyo Chemical Industry Co., Ltd.) ), 2 parts of rubber particles (Stapyloid AC3816N manufactured by Kanto Chemical Co., Ltd.), 2 parts of flame retardant ("HCA-HQ", 10- (2,5-dihydroxyphenyl) -10 -Hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2 탆) (Average particle diameter: 0.5 mu m, SOC2 manufactured by Adomex Co., Ltd., carbon amount per unit area: 0.39 mg / m &lt; 2 &gt;) surface treated with a siloxane-based siloxane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., ) Were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. Subsequently, an adhesive film was produced in the same manner as in Example 1.

&Lt; Example 3 >

10 parts of a bisphenol-type epoxy resin ("ZX1059" manufactured by Shin-Etsu Chemical Co., Ltd., a 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 10 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Manufactured by NIPPON KOGYO CO., LTD., Epoxy equivalent 269) was dissolved by heating in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 17 parts of phenoxy resin A, 17 parts of an active ester compound (&quot; HPC8000-65T &quot;, manufactured by DIC Corporation), a toluene solution of a weight average molecular weight of about 2700, ), 6 parts of a hardening accelerator (4-dimethylaminopyridine, 2% by mass of a solid content MEK solution), 6 parts of a flame retardant ("HCA-HQ" manufactured by Sankyo Kabushiki Kaisha, 10- (2,5-dihydroxyphenyl) 2 parts by weight of 10-hydro-9-oxa-10-phosphapenanthrene-10-oxide, average particle diameter 2 占 퐉), surface treatment with phenylaminosilane coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., And 150 parts of spherical silica (average particle diameter 0.5 mu m, SOC2 manufactured by Adomex Co., Ltd., carbon amount per unit area 0.39 mg / m &lt; 2 &gt;) were uniformly dispersed with a high speed rotary mixer to prepare a resin varnish. Subsequently, an adhesive film was produced in the same manner as in Example 1.

&Lt; Comparative Example 1 &

12 parts of the phenoxy resin A of Example 1 was changed to 10 parts of a bisphenol A phenoxy resin ("E1256B40" manufactured by Mitsubishi Chemical Corporation, MEK solution having a solid content of 40 mass%, epoxy equivalent: 8000, weight average molecular weight: about 50000) , An adhesive film was prepared in exactly the same manner as in Example 1.

&Lt; Comparative Example 2 &

An adhesive film was prepared in exactly the same manner as in Example 2 except that 5 parts of phenoxy resin A of Example 2 was replaced by 5 parts of phenoxy resin B of Synthesis Example 2.

&Lt; Comparative Example 3 &

An adhesive film was prepared in exactly the same manner as in Example 3 except that 17 parts of phenoxy resin A of Example 3 was replaced by 17 parts of phenoxy resin B of Synthesis Example 2.

The results are shown in Tables 1 and 2.

&Lt; Comparative Example 4 &

An adhesive film was prepared in exactly the same manner as in Example 1 except that 12 parts of the phenoxy resin A of Example 1 was changed to 3.6 parts of an anthracene type epoxy resin ("YX8800" manufactured by Mitsubishi Kagaku KK, epoxy equivalent 181) . The structural formula of &quot; YX8800 &quot; is as follows.

&Lt; Comparative Example 5 &

An adhesive film was prepared in exactly the same manner as in Example 1, except that 12 parts of the phenoxy resin A of Example 1 was changed to 43 parts. In Comparative Example 5, when the total amount of the phenoxy resin (A), the epoxy resin (B), and the curing agent is 100 mass%, the phenoxy resin (A) is 18.8 mass% It is beyond the scope of the invention.

The results are shown in Tables 1 and 2.

From the results shown in Tables 1 and 2, Examples 1 to 3 using the curable resin composition of the present invention have low illuminance, sufficient strength, low coefficient of linear thermal expansion, and sufficient fracture elongation. On the other hand, in Comparative Examples 1 to 5, since the curable resin composition of the present invention is not used, when the arithmetic average roughness, the root average squareness roughness, the peel strength becomes small, the coefficient of linear thermal expansion becomes large, And the like.

Claims (17)

A curable resin composition comprising (A) a phenoxy resin having an anthracene structure, (B) an epoxy resin, and (C) a curing agent, wherein the phenoxy resin (A), the epoxy resin (B) Wherein the phenoxy resin (A) is 1 to 15% by mass and the epoxy equivalent of the phenoxy resin (A) is 5000 or more when the total amount is 100% by mass. The curable resin composition according to claim 1, wherein the (A) phenoxy resin has a weight average molecular weight of 8000 to 100000. The curable resin composition according to claim 1, wherein the (A) phenoxy resin further has an unsubstituted or substituted biphenyl structure. The epoxy resin composition according to claim 1, wherein the epoxy resin (B) is at least one selected from the group consisting of a bisphenol epoxy resin, a crystalline bifunctional epoxy resin, a dicyclopentadiene epoxy resin, a naphthalene epoxy resin, &Lt; / RTI &gt; The curable resin composition according to claim 1, wherein the (C) curing agent is selected from the group consisting of a phenol curing agent, a cyanate ester curing agent, an active ester curing agent, and a mixture of these curing agents. The curable resin composition according to claim 1, wherein the (C) curing agent is a cyanate ester curing agent or an active ester curing agent. The positive resist composition according to claim 1, wherein the content of the phenoxy resin (A) is 0.3 to 10% by mass and the content of the epoxy resin (B) is 5 to 100% by mass, based on 100% by mass of the nonvolatile component in the curable resin composition. By mass to 30% by mass, and the content of the (C) curing agent is 3 to 20% by mass. The curable resin composition according to claim 1, further comprising (D) an inorganic filler. The curable resin composition according to claim 8, wherein the inorganic filler (D) has an average particle diameter of 0.01 to 5 탆. The curable resin composition according to claim 8, wherein the content of the inorganic filler (D) is 30 to 90% by mass when the non-volatile component in the curable resin composition is 100% by mass. The curable resin composition according to claim 8, wherein the inorganic filler (D) is silica. A curable resin composition for an insulating layer of a multilayered printed circuit board, which comprises the curable resin composition according to any one of claims 1 to 11. A curable resin composition for a build-up layer of a multilayer printed wiring board, which comprises the curable resin composition according to any one of claims 1 to 11. A sheet-stacked material characterized by comprising the curable resin composition according to any one of claims 1 to 11. A multilayer printed wiring board characterized by comprising an insulating layer obtained by thermosetting the curable resin composition according to any one of claims 1 to 11.  A multilayer printed wiring board characterized by comprising an insulating layer obtained by thermally curing the sheet-laminated material according to claim 14. A semiconductor device comprising the multilayer printed wiring board according to claim 16.