KR102126657B1 - Curable resin composition - Google Patents

Abstract

[Task] The resin flow property (embedding property) in the thin film is excellent, and in the wet roughening process, not only the arithmetic mean roughness of the surface of the insulating layer is low, but also the square mean square root roughness is low, and a plated conductor layer having sufficient peel strength is formed. It is possible to provide a curable resin composition having a low coefficient of linear thermal expansion.
[Solutions] (1) (1-A) Epoxy resin A having two or more kinds of structures selected from biphenyl structure, bixylenol structure, bisphenol acetophenone structure, and bisphenol fluorene structure, and (1-B) As an epoxy resin mixture containing an epoxy resin B other than the epoxy resin A, when the epoxy resin mixture is 100% by mass, the content of the epoxy resin A is 3 to 30% by mass, the epoxy equivalent of the epoxy resin A It provides a curable resin composition, characterized in that it contains the 1500 to 4800 epoxy resin mixture, (2) a curing agent, and (3) an inorganic filler.

Description

Curable resin composition {CURABLE RESIN COMPOSITION}

The present invention relates to a curable resin composition. Further, the present invention relates to a curable resin composition for an insulating layer containing the curable resin composition, a sheet-like laminated material, a multilayer printed wiring board, and a semiconductor device.

In recent years, miniaturization and high-performance of electronic devices have progressed, and in the multilayer printed wiring board, the build-up layer is multi-layered, and miniaturization and high-density wiring are required.

Various attempts have been made. For example, Patent Document 1 discloses using a polymer epoxy resin having a specific structure as a resin composition for a printed wiring board, and improving heat resistance, low water absorption, electrical properties, moldability, flexibility, impact resistance, and adhesion. (Claims and paragraph number 0003, etc.). However, the resin composition of Patent Literature 1 relates to a polymer epoxy resin having an epoxy equivalent of 5000 g/equivalent or more, and the heat resistance is insufficient under 5000 g/equivalent, which is undesirable (paragraph 0016).

Japanese Patent Application Publication No. 2003-252951

The technical problem to be solved by the present invention is excellent in resin flowability (embedding property) in a thin film, as well as low arithmetic average roughness of the insulating layer surface in a wet harmonic process, as well as low square mean square root roughness ( It is to provide a curable resin composition capable of forming a plated conductor layer having low roughness and sufficient peel strength, and having a low coefficient of linear thermal expansion.

The present inventors have studied earnestly to solve the above problems, and as a result, (1) an epoxy resin mixture containing an epoxy resin A having a specific structure and other epoxy resin B, the epoxy resin mixture at 100% by mass When the content of the epoxy resin A is 3 to 30% by mass, the epoxy resin mixture of the epoxy equivalent of 1500 to 4800 epoxy resin mixture, (2) curing agent, and (3) characterized in that it contains an inorganic filler It has been found that the curable resin composition described above is excellent in the embedding properties described above, and can achieve low roughness, high peel strength, and low coefficient of linear thermal expansion, thereby completing the present invention.

That is, the present invention includes the following forms.

[1] (1) (1-A) Epoxy resin A having two or more kinds of structures selected from biphenyl structure, bixylenol structure, bisphenol acetophenone structure, and bisphenol fluorene structure, and (1-B) above As an epoxy resin mixture containing an epoxy resin B other than the epoxy resin A, when the epoxy resin mixture is 100 mass%, the content of the epoxy resin A is 3 to 30 mass%, and the epoxy equivalent of the epoxy resin A Epoxy resin mixture of 1500 to 4800,

(2) curing agent, and

(3) inorganic filler

Curable resin composition characterized in that it contains.

[2] The curable resin composition according to [1], wherein the content of the epoxy resin A when the nonvolatile component in the curable resin composition is 100 mass% is 0.5 to 10 mass%.

[3] The epoxy resin B according to [1] or [2], wherein the (1-B) epoxy resin B is a bisphenol-type epoxy resin, a crystalline bifunctional epoxy resin, a dicyclopentadiene-type epoxy resin, a naphthalene-type epoxy resin, and these epoxy A curable resin composition selected from the group consisting of mixtures of resins.

[4] The curable resin composition according to any one of [1] to [3], wherein the epoxy equivalent of the (1) epoxy resin mixture is 50 to 3000.

[5] The curable resin composition according to any one of [1] to [4], wherein the curing agent (2) is at least one selected from phenol resins, cyanate ester resins, and active ester resins.

[6] The curable resin composition according to any one of [1] to [5], wherein the average particle diameter of the (3) inorganic filler is 0.01 to 5 µm.

[7] The curable resin composition according to any one of [1] to [6], wherein the inorganic filler (3) is surface treated with a surface treatment agent.

[8] The curable resin composition according to any one of [1] to [7], wherein the inorganic filler (3) is silica.

[9] The content of the curing agent (2) in any one of [1] to [8], wherein the content of the curing agent (2) is 1 to 30% by mass, and the ( 3) Curable resin composition whose content of an inorganic filler is 30-90 mass %.

[10] A curable resin composition for an insulating layer of a multilayer printed wiring board, comprising the curable resin composition according to any one of [1] to [9].

[11] A curable resin composition for a build-up layer of a multilayer printed wiring board, comprising the curable resin composition according to any one of [1] to [9].

[12] A sheet-like layered material comprising the curable resin composition according to any one of [1] to [9].

[13] The sheet-like laminate material according to [12], wherein the thickness is 5 to 30 µm.

[14] A multi-layer comprising the curable resin composition according to any one of [1] to [11], or an insulating layer obtained by thermally curing the sheet-like laminate material according to [12] or [13]. Printed wiring board.

[15] A multilayer printed wiring board comprising the insulating layer obtained by thermally curing the sheet-like laminate material according to [12].

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

In addition, the present invention preferably includes the following forms.

[A] (1) (1-A) Epoxy resin A ₁ comprising a bixyleneol structure, a bisphenol acetophenone structure, and a bisphenol fluorene structure, and (1-B) bisphenol type epoxy resin, crystalline bifunctional epoxy An epoxy resin mixture comprising epoxy resin B ₁ selected from the group consisting of resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, and mixtures of these epoxy resins, when the epoxy resin mixture is 100% by mass The epoxy resin mixture having an epoxy equivalent of 50 to 3000, the content of the epoxy resin A ₁ is 5 to 20% by mass, the epoxy equivalent of the epoxy resin A ₁ is 2000 to 4200,

(2) at least one curing agent selected from phenol resins, cyanate ester resins and active ester resins, and

(3) Silica as inorganic filler

Curable resin composition for an insulating layer of a multilayer printed wiring board, characterized by containing the.

The insulating layer of the multilayer printed wiring board prepared by thermosetting the curable resin composition of the present invention has excellent resin flowability (embedding) in a thin film, and not only has low arithmetic average roughness of the surface of the insulating layer in a wet roughening process, but also means square root The roughness is also low, and a plated conductor layer having sufficient peel strength can be formed, and the coefficient of linear thermal expansion is also low.

Particularly, in the present invention, the low roughness and high peel strength can be achieved by using component (1). In addition, in general, an epoxy resin composition containing a relatively large amount of inorganic filler may have voids between conductors stacked inferior to the resin flow in the thin film, and the peel strength is likely to decrease, but the component (1) as in the present invention By using, embedding property and peel strength can be improved.

[Curable resin composition]

The curable resin composition, which is one of the aspects of the present invention, is an epoxy resin having two or more kinds of structures selected from (1) (1-A) biphenyl structure, bixylenol structure, bisphenol acetophenone structure, and bisphenol fluorene structure. An epoxy resin mixture containing A and (1-B) epoxy resin B other than the epoxy resin A, wherein the content of the epoxy resin A when the epoxy resin mixture is 100% by mass is 3 to 30% by mass , The epoxy resin mixture of the epoxy equivalent of 1500 to 4800 epoxy resin,

(2) curing agent, and

(3) inorganic filler

It is a curable resin composition characterized by containing the. Hereinafter, the epoxy resin composition of the present invention will be described in detail.

[Ingredient (1)]

(1-A) Epoxy resin A

The epoxy resin A which can be used in the present invention has two or more kinds of structures selected from biphenyl structures, bixylenol structures, bisphenol acetophenone structures, and bisphenol fluorene structures. Each structure can be represented by the following formulas (1) to (4).

Biphenyl structure

(1)

(One)

Vixylol structure

(2)

(2)

Bisphenol acetophenone structure (refer to Japanese Unexamined Patent Publication No. 2003-252951)

(3)

(3)

(Formula (3) of, R ₁ is may be the same and also different from each other, a group selected from the group consisting of a hydrogen atom, a hydrocarbon group and a halogen atom C _{1 -10,} R ₂ is a hydrogen atom, a C _{1 -} a group selected from the group consisting of a hydrocarbon group and a halogen atom _10, R ₃ is a hydrocarbon group a hydrogen atom or C _{1 -10,} m is an integer from 0 to 5)

Bisphenol fluorene structure (See Japanese Patent Laid-Open No. 2003-252951)

(4)

(4)

Of (formula _(4), R 4 which may be the even phase the same or different, is a group selected from the group consisting of a hydrogen atom, a hydrocarbon group and a halogen atom C _{1 -10,} R ₅ is the same or different from each other in Fig. also good, and a group selected from a hydrocarbon group, or a halogen atom of a hydrogen atom, C _{1 -10,} n is different from Fig may be the the same or different and are an integer of 0 to 4)

In a more preferred form, the formula (3) of, R ₁ is may be also different from the same or different, a hydrocarbon group, a hydrogen atom or a C _{1 -8,} more preferably represents a hydrogen atom or a C _{1 -6,} further preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom, R ₂ is an alkyl group is a hydrogen atom or a C _{1 -8} hydrocarbon group, more preferably a hydrogen atom or a C _{1 -6,} more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom, R ₃ is a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom or an alkyl group C _{1 -8} hydrocarbon group, more preferably a hydrogen atom or a C _{1 -6,} more preferably It is preferably a methyl group, and m is an integer from 0 to 3, more preferably from 1 to 2.

Further, formula (4) of, R ₄ which may be the even phase the same or different, represents a hydrogen atom or a C _{1 -8} hydrocarbon group, more preferably a hydrogen atom or a C _{1 -6,} more preferably hydrogen atom or a methyl group, R ₅ is identical to Fig may be different from each other, a hydrocarbon group a hydrogen atom or a C _{1 -8,} more preferably a hydrogen atom or a methyl group, a hydrogen atom or an alkyl group C _{1 -6,} more preferably one another , Particularly preferably a hydrogen atom, and n may be the same or different from each other, and is an integer of 0 to 3, more preferably 1 to 2.

As the epoxy resin A, specifically, an epoxy resin having three or more structures selected from a biphenyl structure, a bixylenol structure, a bisphenol acetophenone structure, and a bisphenol fluorene structure is preferable, and a bixylenol structure and a bisphenol acetophenone structure And an epoxy resin having a bisphenol fluorene structure, and an epoxy resin having a biphenyl structure, bixylenol structure, bisphenol acetophenone structure and bisphenol fluorene structure. More specifically, in the bisphenol acetophenone structure, in the formula (3), R ₁ is a hydrogen atom, R ₂ is a hydrogen atom, and R ₃ is preferably a methyl group. In the bisphenol fluorene structure, in the formula (4), it is preferable that R ₄ has a hydrogen atom and a methyl group, and R ₅ is a hydrogen atom.

As an example of the manufacturing method of the epoxy resin A, it can be manufactured by reacting the epoxy group of the biphenyl type epoxy resin and the bixylenol type epoxy resin, and the phenol group of bisphenol acetophenone derivative and bisphenol fluorene derivative. Specifically, the ratio of the number of epoxy groups of the biphenyl-type epoxy resin and the bixylenol-type epoxy resin to the number of phenol groups derived from the bisphenol acetophenone derivative and the bisphenolfluorene derivative is preferably 1:1 to 1.5:1, and 1.05: 1 to 1.4:1 are more preferable, and 1.1:1 to 1.3:1 are more preferable. This makes it easy to set the epoxy equivalent of epoxy resin A to 1500 to 4800. The ratio of the number of phenol groups derived from bisphenol acetophenone derivatives to the number of phenol groups derived from bisphenol fluorene derivatives is preferably 1:5 to 1:15, and more preferably 1:7 to 1:10. Thereby, the heat resistance of epoxy resin A can be improved.

The content of the epoxy resin A is 3 to 30 mass%, preferably 4 to 25 mass%, and more preferably 5 to 20 mass% when the epoxy resin mixture as component (1) is 100 mass%. . When the content of the epoxy resin A is 3% by mass or more, low arithmetic average roughness and low square root mean square root roughness are obtained, and if it is 30% by mass or less, the crosslinking site can be sufficiently maintained, and thus low arithmetic average roughness and low square mean square root roughness are obtained. It is also possible to maintain a low coefficient of linear thermal expansion.

The epoxy equivalent of epoxy resin A (mass of resin containing 1 equivalent of epoxy group) is 1500 to 4800 (g/equivalent), preferably 1700 to 4600 (g/equivalent), more preferably 1900 to 4400 (g /Equivalent), more preferably 2000 to 4300 (g/equivalent), particularly preferably 2000 to 4200 (g/equivalent). When the epoxy equivalent of the epoxy resin A is 1500 or more, it becomes low arithmetic mean roughness and low square root mean square root roughness, and if it is 4800 or less, it can sufficiently maintain the crosslinking site, so it also becomes low arithmetic mean roughness and low square mean square root roughness, and also , Can maintain a low coefficient of linear thermal expansion.

Further, the epoxy equivalent of the entire epoxy resin mixture of component (1) is preferably 50 to 3000 (g/equivalent), more preferably 100 to 2000 (g/equivalent), more preferably 150 to 1000 (g/e) Equivalent), particularly preferably 200 to 500 (g/equivalent). Thereby, the crosslinking density of the insulating layer obtained from the curable resin composition becomes sufficient, and it becomes advantageous for low roughness. In addition, the epoxy equivalent can be measured according to JIS K7236 (2001).

When the nonvolatile component in the curable resin composition is 100% by mass, the content of the epoxy resin A is preferably 0.5 to 10% by mass, more preferably 0.5 to 7% by mass, more preferably 0.5 to 5% by mass It is suitable to be %.

(1-B) Epoxy resin B

The epoxy resin B is an epoxy resin other than the epoxy resin A. Preferably, the epoxy resin B is an epoxy resin having two or more epoxy groups in one molecule.

Specific examples of the epoxy resin B include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol-type epoxy resins such as bisphenol AF-type epoxy resins, dicyclopentadiene-type epoxy resins, and phenol nos. Bolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresolno Bolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy And resins, trimethylol-type epoxy resins, halogenated epoxy resins, and crystalline bifunctional epoxy resins. More preferably, the epoxy resin B is selected from the group consisting of bisphenol-type epoxy resins, crystalline bifunctional epoxy resins, dicyclopentadiene-type epoxy resins, naphthalene-type epoxy resins, and mixtures of these epoxy resins. These may be used alone or in combination of two or more.

Among these epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, crystalline bifunctional epoxy resins, dicyclopentadiene-type epoxy resins, naphthalene-type epoxy resins, and mixtures of two or more thereof are preferred from the viewpoint of improving heat resistance. . Specifically, for example, bisphenol A-type and F-type mixed epoxy resins ("ZX1059" manufactured by Shinnitetsu Chemical Co., Ltd.), bisphenol A-type epoxy resins ("Epicoat 828EL" manufactured by Mitsubishi Chemical Co., Ltd.) , ``YL980'', ``jERl009''), bisphenol F type epoxy resin (Mitsubishi Chemical Co., Ltd. ``jER806H'', ``YL983U''), naphthalene type bifunctional epoxy resin (DIC Co., Ltd. ``HP4032'', ``HP4032D ,, "HP4032SS", "EXA4032SS"), naphthalene type 4-functional epoxy resin ("HP4700", "HP4710" manufactured by DIC Corporation), naphthol type epoxy resin ("ESN-475V" manufactured by Shinnitetsu Chemical Co., Ltd.) ), epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Co., Ltd.), biphenyl-type epoxy resin ("NC3000H" manufactured by Nihon Kayaku Co., Ltd., "NC3000L", "NC3100"), Vixylol type epoxy resin (Mitsubishi Chemical Co., Ltd. ``YX4000'', ``YX4000H'', ``YX4000HK'', ``YL6121''), anthracene type epoxy resin (Mitsubishi Chemical Co., Ltd. ``YX8800''), naphthylene ether Type epoxy resin ("EXA-7310" manufactured by DIC Corporation, "EXA-7311", "EXA-731lL", "EXA7311-G3"), glycidyl ester type epoxy resin (manufactured by Nagase Chemtex Co., Ltd.) EX711", "EX721", "R540" manufactured by Purintech Co., Ltd., dicyclopentadiene type epoxy resin ("HP-7200H" by DIC Corporation), and the like.

In addition, the main component structural formula of HP4032SS is as follows.

In addition, the structural formula of NC3000L is as follows.

(n is an integer from 1 to 20)

In addition, the structural formula of YX4000HK is as follows.

(Wherein, Gr is a glycidyl group)

In addition, the structural formula of HP-7200H is as follows.

(Wherein, n is an integer from 1 to 20)

In addition, the structural formula of jERl009 is as follows.

The content of the epoxy resin B is 70 to 97 mass%, preferably 75 to 96 mass%, and more preferably 80 to 95 mass% when the epoxy resin mixture as the component (1) is 100 mass%.

(2) curing agent

(2) As the curing agent, any curing agent can be used as long as it can be cured by crosslinking the epoxy resin mixture, but examples thereof include phenol resins, cyanate ester resins, benzoxazine resins, and active ester resins. Can. Among these, phenol resin, cyanate ester resin and active ester resin can significantly lower the surface roughness of the insulating layer.

The active ester resin that can be used in the present invention is a resin compound having one or more active ester groups in one molecule. Here, "active ester group" means an ester group that reacts with an epoxy resin. The active ester resin can react with an epoxy resin, and a resin compound having two or more active ester groups in one molecule is preferred. In general, a resin compound having two or more ester groups having a high reaction activity in one molecule selected from the group consisting of phenol ester, thiophenol ester, N-hydroxyamine ester and heterocyclic hydroxy compound ester is an active ester resin. It is preferably used as. 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 from 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. Active ester resins obtained from reacting one or two or more selected from phenol compounds, naphthol compounds and thiol compounds with carboxylic acid compounds are more preferred. Even more preferable is an aromatic resin compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group. An aromatic resin compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule and an aromatic compound having a phenolic hydroxyl group, and also having two or more active ester groups in one molecule of the aromatic resin compound. Aromatic resin compounds are particularly preferred. The active ester resin may be linear or multi-branched. Further, if the compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, compatibility with the resin composition can be increased, and if the compound has an aromatic ring, 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 these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred from the viewpoint of heat resistance, and isophthalic acid and terephthalic acid are more preferable. As a thiocarboxylic acid compound, thioacetic acid, thiobenzoic acid, etc. are specifically mentioned.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m -Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone , Trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolac, and the like. Among these, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxy from the viewpoint of improving heat resistance and solubility. Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopenta Dienyl diphenol and phenol novolak are preferred, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, and trihydroxy Benzophenone, tetrahydroxybenzophenone, phloroglusin, benzenetriol, dicyclopentadienyldiphenol, phenol novolak are more preferable, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene , 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, phenol novolak, more preferably, 1,5-dihydroxy Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyldiphenol, and phenol novolak are more preferred, and 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyldiphenol is particularly preferred, and dicyclopentadienyldiphenol is particularly preferred. Specific examples of the thiol compound include benzenedithiol and triazinedithiol.

As an active ester resin, specifically, an active ester resin containing a dicyclopentadienyl diphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylate of phenol novolac, benzoyl of phenol novolac An active ester resin containing a cargo is preferable, and an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadienyldiphenol structure are more preferable. As a commercial product, EXB9451, EXB9460, EXB9460S, HPC8000-65T (made by DIC Corporation) as an active ester resin containing a dicyclopentadienyldiphenol structure, EXB9416-70BK (DIC (DIC ( Co., Ltd.), DC808 (Mitsubishi Chemical Co., Ltd.) as an active ester resin containing phenol novolac acetylate, and YLHl026 (Mitsubishi Chemical Co., Ltd.) as an active ester resin containing phenol novolac benzoylide. Manufacturing) and the like.

Particularly preferred active ester resins are the following formula (I)

(I)

(I)

(In the formula, m is 0 or 1, n is an average value of 0.25 to 1.5, preferably 0.4 to 1.2) and includes a dicyclopentadienyldiphenol structure, X-group and XO-group at the terminal (Here, X is a phenyl group or a naphthyl group which may have a substituent). The weight average molecular weight of the active ester resin is preferably 1500 to 4000, more preferably 2000 to 3000.

Particularly preferred active ester resins have a dicyclopentadienyldiphenol structure represented by the following formula (5), and have X-groups and XO-groups at the terminals (where X is a naphthyl group which may have a substituent). , HPC8000-65T, an active ester resin having a weight average molecular weight of about 2700.

(5)

(5)

(Wherein, m is 0 or 1, n is an average value of 0.4 to 1.2)

The phenol resin is not particularly limited, but biphenyl type phenol resin, naphthalene type phenol resin, phenol novolak resin, naphthylene ether type phenol resin, and triazine skeleton-containing phenol resin are preferred. Specifically, MEH-7700, MEH-7810, and MEH-7851 of biphenyl type phenol resin (manufactured by Meiwa Kasei Co., Ltd.), NHN, CBN, GPH of Naphthalene type phenol resin (manufactured by Nihon Kayaku Co., Ltd.) , SN-170, SN-180, SN-190, SN-475, SN-485, SN-495, SN-375, SN-395 (manufactured by Shinnitetsu Chemical Co., Ltd.), EXB9500 (manufactured by DIC Corporation ), TD2090 of phenol novolak resin (manufactured by DIC Corporation), EXB-6000 of naphthylene ether type phenol resin (manufactured by DIC Corporation), LA-3018, LA-7052, LA of triazine skeleton-containing phenol resin -7054, LA-1356 (manufactured by DIC Corporation), and the like. These may use 1 type or 2 or more types together.

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

(n is an integer from 1 to 20)

In addition, the structural formula of LA-7054 is as follows.

(n is an integer from 1 to 20)

Although there is no restriction|limiting in particular as a cyanate ester resin, A novolak-type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol type cyanate ester resin, and a prepolymer in which these are triazine-ized etc. are mentioned. Specifically, the phenol novolak-type polyfunctional cyanate ester resin represented by the following formula (6) (Lonja Japan Co., Ltd., PT30S: number average molecular weight 380, PT60: number average molecular weight 560), the following formula (7) Bisphenol A cyanate ester resin (produced by Lonja Japan Co., Ltd., BA230S75), which is a prepolymer in which a part or all of the indicated bisphenol A cyanate ester resin is triazineized to become a trimer, dicyclo represented by the following formula (8) And pentadiene cyanate ester resins (manufactured by Lonza Japan Co., Ltd., DT-4000, DT-7000). Specifically, the number average molecular weight is LC-9A/RID-6A manufactured by Shimadzu Corporation, as a measuring device, and Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. as a column. , It can be measured by using a chloroform or the like as a mobile phase at a column temperature of 40°C, and using a calibration curve of standard polystyrene. These may be used alone or in combination of two or more.

(6)

(6)

[Wherein, n is an arbitrary number as an average value (preferably 0 to 20, more preferably 1 to 10)]

(7)

(7)

(8)

(8)

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

The content of the curing agent in the curable resin composition of the present invention is not particularly limited, but from the viewpoint of achieving both low roughness and high peel strength of the insulating layer, when the non-volatile component in the cured resin composition is 100% by mass, 1 It is preferably from 30 to 30% by mass, more preferably from 2 to 20% by mass, and even more preferably from 5 to 15% by mass.

In addition, when the number of epoxy groups in the entire epoxy resin mixture is 1, the number of reactors in the curing agent is preferably 0.2 to 2, more preferably 0.3 to 1.5, and even more preferably 0.4 to 1. Here, "the total number of epoxy groups in the epoxy resin mixture" is a value obtained by dividing the solid content mass of each epoxy resin present in the curable resin composition by the epoxy equivalent, for all epoxy resins. In addition, "reactor" means a functional group capable of reacting with an epoxy group, and "reactor number" is a total value obtained by dividing the solid content mass of the curing agent present in the resin composition by the reactor equivalent.

(3) inorganic filler

Examples of the inorganic filler that can be used in the present invention include silica, alumina, mica, mica, silicate, barium sulfate, magnesium hydroxide, titanium oxide, and the like, silica and alumina are preferred, particularly amorphous silica, Silica such as fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferred, and spherical silica and fused silica are more preferred. Spherical fused silica is more preferable from the viewpoint of improving the fillability of the inorganic filler to the sheet-like laminated material of the present invention containing the curable resin composition. One or two or more inorganic fillers may be used. As commercially available spherical fused silica, "SOC2" and "SOC1" manufactured by Admatex Co., Ltd. are mentioned.

The average particle diameter of the inorganic filler is not particularly limited, but is preferably 5 µm or less, more preferably 3 µm or less, further preferably 1 µm or less, and more preferably 0.8 µm or less from the viewpoint of forming fine wiring on the insulating layer. Is even more preferable, and 0.6 µm or less is particularly preferable. On the other hand, when a curable resin composition is used as a varnish, 0.0 l μm or more is preferable, 0.03 μm or more is more preferable, and 0.07 μm or more is more preferable from the viewpoint of preventing the viscosity of the varnish from rising and handling property falling. And 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 prepared on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter can be measured by making it an average particle diameter. As the measurement sample, one in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba Seisakusho Co., Ltd. may be used.

The content of the inorganic filler is not particularly limited, but when the nonvolatile component in the curable resin composition is 100% by mass from the viewpoint of preventing the sheet-like flexibility of the sheet-like laminated material from deteriorating, the amount of the inorganic filler is 30. It is preferable that it is 90 mass %, 40-85 mass% is more preferable, and 50-85 mass% is still more preferable. In particular, in the present invention, even in a curable resin composition containing 50% by mass or more of an inorganic filler, embedding property and peel strength can be improved.

It is preferable that the inorganic filler is surface-treated (coated) with a coupling agent or the like to improve moisture resistance and dispersibility. As the surface treatment agent (coupling agent), at least one selected from epoxysilane-based coupling agents, aminosilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, organosilazane compounds, and titanate-based coupling agents is preferable. Do. Among these, an aminosilane-based coupling agent is preferred because of its excellent moisture resistance, dispersibility, and properties of a cured product, and a phenylaminosilane-based coupling agent is more preferable. As commercially available products, "KBM403" (3-glycidoxypropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. , Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyl triethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyl trimethoxysilane), Shin-Etsu And ``KBMl03'' (phenyltrimethoxysilane) manufactured by Kagaku Kogyo Co., Ltd., ``SZ-31'' (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[Other ingredients]

The curable resin composition of the present invention includes, as components other than the above-mentioned components, a curing accelerator; Thermoplastic resins; Thermosetting resins such as vinylbenzyl compounds, acrylic compounds, maleimide compounds, and block isocyanate compounds; Flame retardants such as phosphorus-based compounds and metal hydroxides; Organic fillers such as silicone powder, nylon powder, fluorine powder, and rubber particles; Organic solvents; Thickeners such as olben and benton; Defoamers of silicone, fluorine, and polymer; Adhesion imparting agents such as imidazole-based, thiazole-based, triazole-based, and silane coupling agents; Coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, and carbon black; Additives and the like can be appropriately blended.

As the curing accelerator, any curing accelerator can be used as long as it can promote crosslinking and curing of the epoxy resin by the curing agent, but for example, amine compounds, guanidine compounds, imidazole compounds, phosphonium compounds and metal-based curing And accelerators. These may be used alone or in combination of two or more.

The amine compound usable in the present invention is not particularly limited, but trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl) And amine compounds such as phenol and 1,8-diazabicyclo(5,4,0)-undecene (hereinafter abbreviated as DBU). These may be used alone or in combination of two or more.

As an imidazole compound which can be used in the present invention, the following formula (9)

(Wherein, R ₆ to R ₉ which may be the even different, the same, respectively, a hydrogen atom, a halogen atom, a cyano group, a nitro group, formyl group, C _{1 - 20} alkyl, C _{2 - 20} alkenyl, C _{2 - 20} alkynyl group, C _{3 - 20,} an allyl group, C _{4 - 20} alkyl diethoxy group, C _{4 -} group on ₂₀ 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 group, C _{1 -10} is a hydroxy group which may have a hydrocarbon group derived from a good silyl group, epoxy resin) It may be a compound represented by.

More specifically, the imidazole compound is 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1- Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl -S-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-S-triazine, 2,4-diamino-6-[2' -Ethyl-4'-methylimidazolyl-(1')]-ethyl-S-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(l')]-ethyl- S-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl A compound selected from the group consisting of imidazole, 2-phenyl-4-methylimidazole, an imidazole compound and an adduct of an epoxy resin, and 2,4-diamino-6-vinyl-S-triazine. Can. These may be used alone or in combination of two or more.

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

When the total amount of non-volatile components in the curable resin composition is 100 mass%, the content of the curing accelerator is preferably used in the range of 0.005 to 3 mass%, and more preferably in the range of 0.01 to 1 mass%. Do.

Examples of the thermoplastic resin include phenoxy resins, polyvinyl acetal resins, polyimide resins, polyamideimide resins, polyethersulfone resins, cycloolefin polymers and polysulfone resins, and phenoxy resins and poly Vinyl acetal resins are preferred. These may be used alone or in combination of two or more.

The weight average molecular weight in terms of polystyrene in the thermoplastic resin is preferably in the range of 8000 to 70000, more preferably in the range of 10,000 to 60000, and more preferably in the range of 20000 to 60000. The weight average molecular weight in terms of polystyrene in the thermoplastic resin can be measured by gel permeation chromatography (GPC). Specifically, the weight average molecular weight in terms of polystyrene in the thermoplastic resin is LC-9A/RID-6A manufactured by Shimadzu Corporation, as a measuring device, and Shodex K-800P/K manufactured by Showa Denko Co., Ltd. as a column. -804L/K-804L can be measured at a column temperature of 40°C using chloroform or the like as the mobile phase, and calculated using a calibration curve of standard polystyrene. In addition, when the thermoplastic resin is a phenoxy resin, the epoxy equivalent of the phenoxy resin is, for example, 10000 to 20000 (g/equivalent).

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

[Preparation of curable resin composition]

The curable resin composition of the present invention is appropriately mixed with the above components, and if necessary, kneading means such as 3-roll, ball mill, bead mill, sand mill, or high-speed rotary mixer, super mixer, planetary mixer and the like stirring It can be prepared by kneading or mixing by means. Moreover, it can also prepare as a resin varnish by adding the said organic solvent further.

In the curable resin composition of the present invention, since the arithmetic average roughness of the surface of the insulating layer is not only low, but also the square root mean square roughness is low, and a plated conductor layer having sufficient peel strength can be formed, in the manufacture of a multilayer printed wiring board, a multilayer print It can be used suitably as a curable resin composition for insulating layers of a 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 multilayer printed wiring board that forms a conductor layer by plating), and also a curable resin composition for a build-up layer of a multilayer printed wiring board. It is suitable as.

Although it does not specifically limit as the form of the curable resin composition of this invention, It can apply to sheet-like laminated materials, such as an adhesive film and a prepreg, and a circuit board (lamination board use, multilayer printed wiring board use, etc.). Although the resin composition of the present invention may be applied to a circuit board in a varnish state to form an insulating layer, industrially, it is generally preferred 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 resin composition is preferably 40 to 150°C from the viewpoint of lamination of the sheet-like laminated material.

[Multi-layer printed wiring board]

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

Here, the conditions of the thermosetting may be appropriately selected according to the type and content of the epoxy resin in the curable resin composition, for example, the curing temperature is 90 to 220°C, preferably 160 to 210°C, and the curing time is It is carried out by heating at 10 to 180 minutes, preferably 20 to 120 minutes. In addition, heat curing may be performed in two steps.

Here, the coefficient of linear thermal expansion (JIS K7197) of the insulating layer is preferably 20 ppm/°C or less, and more preferably 19 ppm/°C or less, as measured by an average linear thermal expansion coefficient of 25 to 150°C. Although there is no restriction|limiting in particular in a lower limit, it is 4 ppm/degreeC normally. Thereby, deformation of an insulating layer (build-up layer) and a 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. Plasma treatment etc. are mentioned as dry conditioning treatment. The wet roughening treatment is performed, for example, by applying various treatment liquids. And a method of performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. Therefore, the treatment liquid may be a kit of these swelling liquids, oxidizing agents, or neutralizing liquids. The wet roughening treatment is preferable in that it can process a large area or multiple sheets at once and has high productivity.

The swelling treatment with a swelling solution is carried out by immersing the insulating layer in a swelling solution at 50 to 80°C for 5 to 20 minutes (preferably at 55 to 70°C for 8 to 15 minutes). As a swelling liquid, an alkali solution, surfactant solution, etc. are mentioned, for example, Preferably it is an alkali solution. As said alkali solution, sodium hydroxide solution, potassium hydroxide solution, etc. are mentioned, for example. As a commercially available swelling liquid, for example, Swelling Dip Securiganth P (Swelling Dip Securiganth P) manufactured by Atotech Japan Co., Ltd., Swelling Dip Securiganth SBU (SBU) ) And the like.

The roughening treatment with an oxidizing agent is carried out by immersing the insulating layer in an oxidizing agent solution at 60 to 80°C for 10 to 30 minutes (preferably at 15 to 25 minutes at 70 to 80°C). Examples of the oxidizing agent include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide, bichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and the like. Further, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. As a commercially available oxidizing agent, alkaline permanganic acid solutions, such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd., and Dojing Solutions Securigant P, are exemplified.

The neutralization treatment with the neutralization solution is carried out by immersion in a neutralization solution at 30 to 50°C for 3 to 10 minutes (preferably at 35 to 45°C for 3 to 8 minutes). An acidic aqueous solution is preferable as the neutralizing solution, and commercially available products include Reduction Solucine Securigant P manufactured by Atotech Japan Co., Ltd.

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

The surface roughness of the surface of the insulating layer after the roughening treatment is preferably 350 nm or less, more preferably 300 nm or less, even more preferably 200 nm or less, and more preferably 100 nm for improving the formation of fine wiring. It is particularly preferable to be the following. Although there is no limitation on the lower limit of the arithmetic mean roughness Ra, it is generally 10 nm or more, 40 nm or more, 70 nm or more, and the like. The square root roughness (Rq) is preferably 450 nm or less, more preferably 350 nm or less, even more preferably 250 nm or less, and particularly preferably 150 nm or less. The lower limit of the square root mean square roughness (Rq) is not limited, but is generally 20 nm or more, 50 nm or more, 90 nm or more. In addition, since the local mean square root roughness (Rq) reflects the local state of the surface of the insulating layer, it can be confirmed by grasping Rq that it is a more compact and smooth insulating layer surface, and the peel strength is stabilized. This corresponds to the surface roughness of the insulating layer after heat-curing and curing the curable resin composition.

The peel strength is preferably 0.45 kgf/cm (4.41 N/cm) or more, and 0.50 kgf/cm (4.90 N/cm) or more, in order to sufficiently adhere the insulating layer to a layer adjacent thereto, for example, a conductor layer. It is more preferable. The higher the upper limit of the peel strength, the better, and is not particularly limited, but is generally 1.5 kgf/cm (14.7 N/cm) or less, 1.2 kgf/cm (11.8 N/cm) or less, 1.0 kgf/cm (9.81 N/cm) or less , 0.8 kgf/cm (7.85 N/cm) or less.

[Sheet-like laminated material]

The sheet-like laminated material used in the present invention is a sheet-like material before curing in which the curable resin composition is layered. The sheet-like laminated material is prepared by a method known to those skilled in the art, for example, a resin varnish in which a resin composition is dissolved in the above-described organic solvent, and the resin varnish is applied to a support using a die coater or the like, and further heated or The organic solvent can be dried by hot air spraying or the like to form a resin composition layer (sheet-like layered material) on the support, thereby producing a sheet-like layered material with a support. Moreover, the sheet-like laminated material can also be made into a prepreg by impregnating and drying a resin varnish with a sheet-like reinforcing base material such as a glass cloth by a hot melt method or a solvent method. Moreover, the sheet-like laminated material with a support body may be called an adhesive film.

Drying conditions are not particularly limited, and the content of the organic solvent in the resin composition layer is dried so as to be 10% by mass or less, preferably 5% by mass or less. Depending on the amount of the organic solvent in the varnish and the boiling point of the organic solvent, the resin composition layer can be formed, for example, by drying the varnish containing 30 to 60% by mass of the organic solvent at 50 to 150° C. for about 3 to 10 minutes. Can.

Although the thickness of the obtained sheet-like laminated material is not particularly limited, for example, a range of 1 to 150 μm is preferable, a range of 2 to 100 μm is more preferable, and a range of 3 to 50 μm is more preferable, The range of 5-30 micrometers is especially preferable.

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

[Support]

Examples of the support that can be used in the present invention include plastic films and metal foils. Specifically, as the plastic film, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, acrylic, cyclic polyolefin, triacetyl cellulose, polyether Sulfide, polyether ketone, polyimide, and the like. Among these, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable, and an inexpensive and readily available polyethylene terephthalate film is preferable.

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

A plastic film is preferred from the viewpoint of versatility, and when a plastic film is used, it is preferable to use a support having a release treatment on a surface in contact with a layer containing a curable resin composition in order to improve peelability. The mold release agent used for the mold release treatment is not particularly limited as long as the layer containing the curable resin composition can be peeled from the support, and examples thereof include silicone type mold release agents, alkyd resin type mold release agents, polyolefin resins, urethane resins, and fluorine resins. have. In addition, a commercially available plastic film with a release layer may be used as the release-treated support, and preferably SK-1, AL-, which are PET films having a release layer containing an alkyd resin-based release agent as a main component, are preferred. 5, AL-7 (manufactured by Lintec Co., Ltd.) and the like. Further, the plastic film may be subjected to a matte treatment or a corona treatment, or a release layer may be formed on the treatment 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 removal.

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

The protective film that can be used in the present invention may be formed for the purpose of preventing adhesion of dust or the like to a layer containing a curable resin composition. As the protective film, a plastic film such as a support can be used. In addition, the protective film may be subjected to a surface treatment such as mud treatment or corona treatment, or may be subjected to the release treatment as described above. The thickness of the protective film is preferably 3 to 30 μm, and more preferably 5 to 20 μm.

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

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

First, a sheet-like laminated material is laminated (laminated) on one 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. In addition, a circuit board here means that the conductor layer (circuit) by which the pattern was processed is formed in one surface or both surfaces of the board|substrate as mentioned above. In addition, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits). Is included. In addition, roughening treatment may be previously performed on the surface of the conductor layer by blackening treatment, copper etching, or the like.

In the above laminate, when the sheet-like laminated material has a protective film, after removing the protective film, if necessary, preheat the sheet-like laminated material and circuit board, and press and heat the sheet-like laminated material to the circuit board. Laminate. In the sheet-like laminated material of the present invention, a method of laminating to a circuit board under reduced pressure by a vacuum lamination method is suitably used. The conditions of the laminate are not particularly limited, but, for example, the pressure is reduced for about 10 to 120 seconds at an air pressure of 20 mmHg (26.7 hPa) or less, and then the compression temperature (laminate temperature) is preferably 70 to 140°C, and the compression pressure ( Lamination pressure) is preferably 0.1 to 1.5 MPa, more preferably 0.5 to 1.2 MPa, and it is preferable to laminate with a pressing time (laminate time) of preferably 5 to 180 seconds. In addition, the method of lamination may be a batch type or a continuous type in a roll. Vacuum lamination can be carried out using a commercially available vacuum laminator. Commercial vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo Morton Co., Ltd., a vacuum pressurized laminator manufactured by Myeonggi Seisakusho, a roll-type dry coater manufactured by Hitachi Industries, and Hitachi Aishi Co., Ltd.( Note) Production vacuum laminator, etc. are mentioned.

Thereafter, in the case of peeling the support after cooling to around room temperature, the insulating layer can be formed on the circuit board by peeling and thermosetting the resin composition to form a cured product. The conditions for thermal curing may be appropriately selected according to the type and content of the resin component in the resin composition, but for example, the curing temperature is 100 to 220°C, preferably 160°C to 210°C, and the curing time is 20 minutes to 180 minutes. It is carried out by heating at minutes, preferably 30 to 120 minutes. In addition, heat curing may be performed in two steps. After forming the insulating layer, if the support is not peeled off before curing, it may be peeled off as necessary.

Further, the sheet-like laminated material may be laminated on one or both sides of the circuit board using a vacuum press machine. The lamination process of heating and pressurizing under reduced pressure can be performed using a general vacuum hot press machine. For example, it can be carried out by pressing a metal plate such as a heated SUS plate from the support side. The press conditions are at a temperature of 70 to 250°C, preferably 100 to 230°C, and the degree of decompression is usually reduced to 0.0lMPa or less, preferably 0.00lMPa or less, and the press pressure ranges from 0.5 to 4MPa and the press time is increased. It is preferable to carry out for 30 to 150 minutes. Heating and pressurization may be performed in one step, but it is preferable to divide the conditions into two or more steps from the viewpoint of controlling the leakage of the resin. For example, the first press is performed at a temperature of 70 to 150° C., the press pressure is in the range of 0.1 to 1.5 MPa, and the second step press is performed at a temperature of 150 to 200° C. and the pressure is 0.5 to 4 MPa. It is preferred. It is preferable to perform the time of each step between 20 and 120 minutes. In this way, the insulating layer can be formed on the circuit board by thermally curing the resin composition layer. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Myeonggi Seisakusho Co., Ltd.), VHl-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like. .

Next, a via hole or a through hole may be formed by drilling the insulating layer formed on the circuit board. The drilling may be performed by known methods such as, for example, drilling, laser, plasma, or a combination of these methods, if necessary, but drilling by lasers such as a carbon dioxide gas laser or a YAG laser may be used. This is the most common method. If the support is not peeled off before drilling, it is peeled off here.

Next, the above roughening treatment is performed on the surface of the insulating layer, and a conductor layer can be 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 opposite to the conductor layer, and a method of forming a conductor layer only by electroless plating. As a method of forming a pattern thereafter, for example, a subtractive method, a semi-additive method, or the like known to those skilled in the art can be used, and a multi-layered print in which a build-up layer is stacked in multiple stages by repeating the series of steps described above multiple times. It becomes a wiring board. In the present invention, since it has low roughness and high 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 at a conduction point of a multilayer printed wiring board that can be used in the present invention. The "conduction point" is "a place for transmitting an electric signal in a multi-layer printed wiring board", and the place may be a surface or a buried place. Moreover, when conducting, a part of the conductor layer may be a conductive part such as a connector other than that. The term "semiconductor chip" is not particularly limited as long as it is an electrical circuit element made of a semiconductor.

The method of mounting a semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer (BBUL) The mounting method by, an anisotropic conductive film (ACF) mounting method, a non-conductive film (NCF) mounting method, etc. are mentioned.

Example

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to these examples. In addition, in the following description, "parts" means "parts by mass" unless otherwise specified, and "%" means "mass%" unless otherwise specified.

<Measurement method, evaluation method>

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

[Preparation of Sample for Measuring Peel Strength, Arithmetic Average Roughness (Ra Value), Square Mean Square Root Roughness (Rq Value)]

(1) Treatment of the base of the laminated board

Epoxy resin double-sided copper-clad laminated board (18 μm thick copper foil, 0.3 mm thick substrate, R5715ES manufactured by Matsushita Denko Co., Ltd.) was etched 1 μm with CZ8100 manufactured by Mack Co. Harmony treatment was performed.

(2) Lamination of adhesive film

The adhesive films prepared in Examples and Comparative Examples were laminated on both sides of the above-mentioned roughened epoxy resin double-sided copper-clad laminate using a batch vacuum press laminator MVLP·500 (manufactured by Myunggi Seisakusho). The laminate was pressure-reduced for 30 seconds to set the air pressure to 13 hPa or less, and then pressed for 30 seconds at 100° C. and a pressure of 0.74 MPa.

(3) curing of the resin composition

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

(4) Harmony treatment

The laminated plate on which the insulating layer was formed was swelled in a distilled glycol monobutyl ether containing Swelling Dip Securigant P (glycol ethers, aqueous solution of sodium hydroxide) of Atotech Japan Co., Ltd. at 60°C. It was immersed for 10 minutes (Example 1, Comparative Examples 1, 4 and 5) and 10 minutes (Examples 2 and 3 and Comparative Examples 2 and 3). Next, as a conditioning solution, Atotech Japan Co., Ltd. outlet rate compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) at 80°C for 15 minutes (Example 1, Comparative Examples 1, 4) , 5), and immersed for 20 minutes (Examples 2 and 3 and Comparative Examples 2 and 3). Finally, as a neutralizing solution, Atotech Japan Co., Ltd. was immersed in a reduction solucine securigant P (aqueous solution of sulfuric acid) at 40°C for 5 minutes. After drying at 80°C for 30 minutes, this substrate was used as evaluation substrate A.

(5) Plating by semi-additive method

The evaluation substrate 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 heating at 150° C. for 30 minutes, annealing treatment was performed, an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing treatment was performed at 190°C for 60 minutes. This substrate was designated as evaluation substrate B.

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

The evaluation substrate A was measured using a non-contact surface roughness machine (WYKO NT3300 manufactured by Vicoins Tsurumtsu Co., Ltd.), a VSI contact mode, and a Ra value by a value obtained by setting the measurement range to 121 μm×92 μm by a 50-fold lens. , Rq value was obtained. It measured by obtaining the average value of 10 points each.

[Measurement of peel strength (peel strength) of the plated conductor layer]

On the conductor layer of the evaluation board B, a sheath of 10 mm in width and 100 mm in length was cut out, and this one end was peeled off and held with a strainer (T.S.E., Autocomm Tester AC-50C-SL), The load (kgf/cm (N/cm)) when peeling 35 mm in the vertical direction at a rate of 50 mm/min in room temperature (25° C.) was measured.

[Measurement of coefficient of linear thermal expansion (CTE)]

The adhesive films obtained in Examples and Comparative Examples were cured by heating at 200° C. for 90 minutes, and peeled from the PET film as a support to obtain a cured sheet. The cured product was cut into a test piece having a width of 5 mm, a length of 15 mm, and a thickness of 30 mm, and a thermomechanical analysis was performed by a tensile weighting method using a thermomechanical analysis device Thermo P1us TMA8310 (manufactured by Rigaku Co., Ltd.). After attaching the test piece to the device, it was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5°C/min. The average linear thermal expansion coefficient (ppm) from 25°C to 150°C in the second measurement was calculated.

[Evaluation of Resin Landfill]

(1) Substrate treatment of substrate

IPC MULTI-PURPOSE TEST BOARD NO. on a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 35㎛, substrate thickness 0.3mm, manufactured by Matsushita Denko Co., Ltd. R5715ES). A pattern of IPC B-25 (line/space=175/175um comb pattern (residual rate 50%)) was formed, and both surfaces were immersed in CZ8100 manufactured by Mack Co., Ltd. to perform a roughening treatment on the copper surface. It was carried out.

(2) Lamination of adhesive film

The adhesive films prepared in Examples and Comparative Examples were laminated so as to come into contact with the resin composition surface using a batch-type vacuum press laminator MVLP-500 (manufactured by Myunggi Seisakusho). The laminate was decompressed for 30 seconds to reduce the air pressure to 13 hPa or less, and then was pressed for 30 seconds at 120° C. and a pressure of 0.74 MPa. Subsequently, hot pressing was performed for 60 seconds at 120°C under a pressure of 0.5 MPa.

(3) curing of the resin composition

After lamination, the PET film as a support was peeled off, and the resin composition was thermally cured at 100°C for 30 minutes and then at l80°C for 30 minutes to form an insulating layer.

(4) Evaluation of the embedding property of the resin surface

The insulation layer on the comb pattern (retention ratio 50%) of line/space = 175/175 µm was observed from the surface with a micro-optical microscope, and the buried without voids was set to &quot;○&quot; This thing was set as "x".

<Synthesis Example 1>

Synthesis of epoxy resin a ₁ having a bixylenol structure, a bisphenol acetophenone structure, and a bisphenol fluorene structure

To the reaction vessel, 222 g of bixyleneol type epoxy resin (YX4000 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), 15 g bisphenol acetophenone (phenolic hydroxyl group equivalent 145), biscresol fluorene (manufactured by JFE Chemical Co., Ltd., phenol Sex hydroxyl equivalent 190) 170 g, cyclohexanone 150 g was added and stirred to dissolve. Subsequently, 0.5 g of a tetramethylammonium chloride solution was added dropwise and reacted at 180° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, epoxy resin a ₁ was obtained by filtration using a filter cloth and dilution with a solvent.

Epoxy equivalent: 2120

1:1 solution of 40% by mass of MEK and cyclohexanone

Further, epoxy resin was a ₁ is formed in a skeleton having a three following structure.

<Synthesis Example 2>

Beak structure xylenol, bisphenol acetophenone structure, and bisphenol fluorene synthesis of an epoxy resin ₂ having a fluorene structure

To the reaction vessel, 203 g of bisyllenol-type epoxy resin (YX4000 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), 15 g bisphenol acetophenone (phenolic hydroxyl group equivalent 145), biscresol fluorene (manufactured by JFE Chemical Co., Ltd., phenol Sex hydroxyl equivalent 190) 170 g, cyclohexanone 150 g was added and stirred to dissolve. Subsequently, 0.5 g of a tetramethylammonium chloride solution was added dropwise and reacted at 180° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, epoxy resin a ₂ was obtained by filtering using a filter cloth and diluting with a solvent.

Epoxy equivalent: 4120

A 1:1 solution of 35% by mass of MEK and cyclohexanone

In addition, the epoxy resin a ₂ was formed of a skeleton having the following three structures.

<Synthesis Example 3>

Synthesis of a biphenyl structure, the beak structure xylenol, bisphenol acetophenone structure, and bisphenol fluorene epoxy resin having a fluorene structure, a ₃

In the reaction vessel, a 1:1 mixture of a biphenyl type epoxy resin and a bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. YL6121H, epoxy equivalent 175) 192 g, bisphenol acetophenone (phenolic hydroxyl group equivalent 145) 15 g, bisphenol 157 g of fluorene (phenolic hydroxyl group equivalent 175) and 150 g of cyclohexanone were added and dissolved by stirring. Subsequently, 0.5 g of a tetramethylammonium chloride solution was added dropwise and reacted at 180° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, epoxy resin a ₃ was obtained by filtration using a filter cloth and dilution with a solvent.

Epoxy equivalent: 3980

Cyclohexanone solution with 35% by mass solid content

Further, the epoxy resin a ₃ was formed in a skeleton having a structure in which four.

<Example 1>

10 parts of bisphenol-type epoxy resin ("ZX1059" manufactured by Shin-Nitetsu Chemical Co., 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), crystalline bifunctional epoxy resin (Mitsubishi Chemical Co., Ltd. ) Preparation ``YX4000HK'', epoxy equivalent 185) 10 parts, dicyclopentadiene type epoxy resin (DIC Corporation ``HP-7200H'', epoxy equivalent 275) 20 parts were dissolved in 40 parts of solvent naphtha while stirring and heating. After cooling to room temperature (25°C), there are 12 parts of epoxy resin a ₁ , a triazine skeleton-containing phenol resin (curing agent, MEK solution with 60% solid content of hydroxyl equivalent of "LA-7054" manufactured by DIC Corporation 125) 12 parts, naphthalene-type curing agent (Shin-Nitetsu Chemical Co., Ltd. ``SN-485'' hydroxyl equivalent 215 solid content 60% MEK solution) 15 parts, curing accelerator (4-dimethylaminopyridine (DMAP), solid content 2% by mass MEK solution) 3 parts, flame retardant ("HCA-HQ" manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10- Spherical silica (average particle diameter 0.5 µm, Admatex Co., Ltd.) surface-treated with 2 parts of oxide, average particle diameter 2 µm, phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., ``KBM573'') Manufacture "SOC2") 225 parts were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. Subsequently, on the release surface of a polyethylene terephthalate film with release treatment ("AL5" manufactured by Lintec Co., Ltd., 38 µm thick, and "PET501010", 50 µm thick, for producing cured products for measurement of linear thermal expansion coefficient (CTE)), The resin varnish was uniformly applied so that the thickness of the resin composition layer after drying was 30 μm, and dried at 80 to 120° C. (average 100° C.) for 4 minutes to prepare an adhesive film. In addition, Example 1 is a reference example of the present invention.

<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 185), 5 parts, biphenyl type 12 parts of epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269) was dissolved by heating while stirring in 30 parts of solvent naphtha. After cooling to room temperature (25°C), 4 parts of the epoxy resin a ₂ therein, bisphenol A type cyanate ester resin ("BA230S75" manufactured by Lonza Japan Co., Ltd., cyanate equivalent weight 232, MEK of 75% by mass non-volatile content) Solution) 20 parts, phenol novolak type polyfunctional cyanate ester resin ("PT30S" manufactured by Lonja Japan Co., Ltd., cyanate equivalent 133, MEK solution of 85% by mass of non-volatile content) 6 parts, curing accelerator (4-dimethylamino Pyridine, 2 parts by weight of MEK solution of solid content) 1 part, curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt(III)acetylacetonato (Co(III)Ac), 3 parts of solid content MEK solution), rubber Particles (Kantsu Kasei Co., Ltd., Stapyroid AC3816N) 2 parts, flame retardant (Sanko Co., Ltd. ``HCA-HQ'', 10-(2,5-dihydroxyphenyl)-10-hydro-oxa-10 -Phosphaphenanthrene-10-oxide, 2 parts of average particle diameter, 2 parts, spherical silica (average particle diameter 0.5) surface-treated with a phenylaminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 100 µm, "SOC2" manufactured by Admatex Co., Ltd. was mixed and 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.

<Example 3>

10 parts of bisphenol type epoxy resin ("ZX1059" manufactured by Shinnitetsu Chemical Co., 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), dicyclopentadiene type epoxy resin (DIC Corporation Preparation "HP-7200H"), 12 parts of epoxy equivalent 275) It melt|dissolved by heating, stirring 30 parts of solvent naphtha. After cooling to room temperature (25° C.), 15 parts of epoxy resin a ₃ therein, an active ester compound ("HPC8000-65T" manufactured by DIC Corporation, weight average molecular weight of about 2700, non-volatile content of active group equivalent of 223 65 mass % Toluene solution) 35 parts, curing accelerator (4-dimethylaminopyridine, MEK solution of 2% by mass solid content) 6 parts, flame retardant ("HCA-HQ" manufactured by Sanko Corporation, 10-(2,5-dihydride) Roxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2 µm) 2 parts, phenylaminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., 「KBM573 ”) 150 parts of spherical silica (average particle diameter 0.5 µm, "SOC2" manufactured by Admatex Co., Ltd.) surface-treated with a high-speed rotary mixer and uniformly dispersed to prepare a resin varnish. Subsequently, an adhesive film was produced in the same manner as in Example 1.

<Comparative Example 1>

Example 1 Epoxy resin a ₁ 12 parts of phenoxy resin (manufactured by Mitsubishi Chemical (Co., Ltd.) "YX6954BH30" bisphenol acetophenone structure containing, one of a solid content of 30 wt% MEK and cyclohexanone: 1 solution, an epoxy equivalent 13000) An adhesive film was produced in exactly the same manner as in Example 1 except that it was changed to 15 parts.

<Comparative Example 2>

Example 2 Epoxy resin a ₂ 4 parts of a phenoxy resin (manufactured by Mitsubishi Chemical (Co., Ltd.) "YX6954BH30" bisphenol acetophenone structure containing, one of a solid content of 30 wt% MEK and cyclohexanone: 1 solution, an epoxy equivalent 13000) An adhesive film was produced in exactly the same manner as in Example 2, except that it was changed to 5 parts.

<Comparative Example 3>

Exemplary epoxy resin of Example ₃ a 3 15 parts of a phenoxy resin (manufactured by Mitsubishi Chemical (Co., Ltd.) "YX6954BH30" bisphenol acetophenone structure containing, one of a solid content of 30 wt% MEK and cyclohexanone: 1 solution, an epoxy equivalent 13000) An adhesive film was produced in exactly the same manner as in Example 3, except that it was changed to 10 parts.

<Comparative Example 4>

Example 1 Epoxy resin a ₁ 12 parts of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical (Co., Ltd.) "jERl009", epoxy equivalent: 2740, solid content 40% by weight of MEK and cyclohexanone 1: 1 solution) 12 parts An adhesive film was produced in exactly the same manner as in Example 1 except that it was changed.

<Comparative Example 5>

In Example 1 by exactly the same way as in Example 1 except that the addition amount of the epoxy resin a ₁ was changed from 12 parts to 50 parts of an adhesive film was produced.

Table 1 and Table 2 show the results.

[ Table 1 ]

[ Table 2 ]

As a result of Tables 1 and 2, in Examples 2 and 3 using the curable resin composition of the present invention, low roughness, sufficient peel strength, low coefficient of linear thermal expansion, and resin embedding property are good. On the other hand, in Comparative Examples 1 to 5, since the curable resin composition of the present invention was not used, the arithmetic mean roughness, square mean square root roughness increased, peel strength was small, and linear thermal expansion coefficient was also increased.

Claims (16)

(1) (1-A) Epoxy resin A having two or more kinds of structures selected from biphenyl structure, bisilenol structure, bisphenol acetophenone structure, and bisphenol fluorene structure, and (1-B) the epoxy resin A As an epoxy resin mixture containing an epoxy resin B other than the above, when the epoxy resin mixture is 100 mass%, the content of the epoxy resin A is 3 to 30 mass%, and the epoxy equivalent of the epoxy resin A is 1500 to 4800 Phosphorus epoxy resin mixture,
(2) at least one curing agent selected from cyanate ester resins and active ester resins, and
(3) inorganic filler
Curable resin composition characterized in that it contains. The curable resin composition according to claim 1, wherein the content of the epoxy resin A when the nonvolatile component in the curable resin composition is 100 mass% is 0.5 to 10 mass%. The (1-B) epoxy resin B is a bisphenol type epoxy resin, a crystalline bifunctional epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, and a mixture of these epoxy resins according to claim 1 or 2. Curable resin composition selected from the group consisting of. The curable resin composition according to claim 1 or 2, wherein the epoxy equivalent of (1) the epoxy resin mixture is 50 to 3000. The curable resin composition according to claim 1 or 2, wherein the average particle diameter of the (3) inorganic filler is 0.01 to 5 µm. The curable resin composition according to claim 1 or 2, wherein the (3) inorganic filler is surface-treated with a surface treatment agent. The curable resin composition according to claim 1 or 2, wherein the (3) inorganic filler is silica. The content of the curing agent (2) is 1 to 30% by mass, and the content of the inorganic filler (3) according to claim 1 or 2, wherein the nonvolatile component in the curable resin composition is 100% by mass. This 30-90 mass% curable resin composition. A curable resin composition for an insulating layer of a multilayer printed wiring board, comprising the curable resin composition according to claim 1. A curable resin composition for a build-up layer of a multilayer printed wiring board, comprising the curable resin composition according to claim 1. A sheet-like laminate material comprising the curable resin composition according to claim 1 or 2. The sheet-like laminated material according to claim 11, having a thickness of 5 to 30 µm. A multilayer printed wiring board comprising an insulating layer obtained by thermally curing the curable resin composition according to claim 1 or 2. A multilayer printed wiring board comprising the insulating layer obtained by thermally curing the sheet-like laminated material according to claim 11. A semiconductor device comprising the multilayer printed wiring board according to claim 14. delete