JP2016196549A - Resin composition for printed wiring board, prepreg, resin substrate, metal clad laminated board, printed wiring board, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for a printed wiring board, a prepreg and a resin substrate for achieving a printed wiring board having a fine circuit dimension and excellent insulation reliability under high temperature and high humidity conditions, and a printed wiring board and a semiconductor device having excellent insulation reliability under high temperature and high humidity conditions.SOLUTION: The resin composition for a printed wiring board of the present invention is a thermosetting resin composition to be used for forming an insulation layer in a printed wiring board; and the composition comprises a maleimide compound (A), in which the maleimide compound (A) comprises at least a bismaleimide compound (A1) represented by formula (a) below.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for a printed wiring board, a prepreg, a resin substrate, a metal-clad laminate, a printed wiring board, and a semiconductor device.

In recent years, along with the demand for higher functionality of electronic devices, the integration of electronic components and the mounting of high-density packaging have progressed, and the miniaturization of semiconductor devices used in these electronic devices has rapidly progressed. ing. A printed wiring board used for a semiconductor device is required to have a high-density and fine circuit.
As a method for forming a fine circuit, an SAP (semi-additive process) method has been proposed. In the SAP method, first, a roughening treatment is performed on the surface of the insulating layer, and an electroless metal plating film serving as a base is formed on the surface of the insulating layer. Next, the non-circuit forming portion is protected by the plating resist, and the copper thickness of the circuit forming portion is thickened by electrolytic plating. Thereafter, the plating resist is removed, and the electroless metal plating film other than the circuit forming portion is removed by flash etching, thereby forming a circuit on the insulating layer. In the SAP method, since the metal layer laminated on the insulating layer can be thinned, finer circuit wiring is possible.

  The semiconductor device is formed, for example, by mounting a semiconductor element on a printed wiring board. As a technique related to such a printed wiring board, for example, one described in Patent Document 1 below can be cited. Patent Document 1 contains a thermosetting resin having a dihydrobenzoxazine ring and a thermosetting resin having a maleimide ring as essential components, and the content ratio of the thermosetting resin having a maleimide ring has a dihydrobenzoxazine ring. The printed wiring board using the thermosetting composition characterized by being 3-30 weight% with respect to the total amount of the thermosetting resin and the thermosetting resin which has a maleimide ring is described.

JP-A-10-259248

  A semiconductor device formed by mounting a semiconductor element on a printed wiring board is required to have excellent insulation reliability between wirings. Such a requirement is particularly noticeable with the recent increase in wiring density of printed wiring boards. However, according to the study by the present inventors, it has been clarified that it is difficult to obtain sufficient insulation reliability of the printed wiring board under high temperature and high humidity with the technique described in Patent Document 1.

（上記式（ａ）において、Ｑは炭素数６以上の２価の直鎖状、分枝鎖状または環状の脂肪族炭化水素基であり、Ｐは２価の原子または有機基であり、ｎは１以上１０以下の整数である） According to the present invention,
A thermosetting resin composition used for forming an insulating layer in a printed wiring board,
Including a maleimide compound (A),
There is provided a printed wiring board resin composition in which the maleimide compound (A) includes at least a bismaleimide compound (A1) represented by the following formula (a).

(In the above formula (a), Q is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 6 or more carbon atoms, P is a divalent atom or organic group, and n Is an integer from 1 to 10.

  Furthermore, according to this invention, the prepreg formed by impregnating a fiber base material with the said resin composition for printed wiring boards is provided.

  Furthermore, according to this invention, the resin substrate containing the hardened | cured material of the said prepreg is provided.

  Furthermore, according to the present invention, there is provided a metal-clad laminate in which a metal foil is provided on one side or both sides of a cured product of the prepreg or a cured product of a laminate obtained by laminating two or more prepregs.

  Furthermore, according to the present invention, there is provided a printed wiring board that is obtained by processing a circuit on the resin substrate or the metal-clad laminate, and is provided with one or more circuit layers.

  Furthermore, according to the present invention, there is provided a semiconductor device in which a semiconductor element is mounted on the circuit layer of a printed wiring board.

  According to the present invention, a resin composition for a printed wiring board, a prepreg, a resin substrate, and a high temperature and high humidity environment that can realize a printed wiring board having fine circuit dimensions and excellent insulation reliability under high temperature and high humidity conditions. It is possible to provide a printed wiring board and a semiconductor device which are excellent in insulation reliability.

It is sectional drawing which shows an example of a structure of the metal-clad laminated board in this embodiment. It is sectional drawing which shows an example of a structure of the printed wiring board in this embodiment. It is sectional drawing which shows an example of a structure of the printed wiring board in this embodiment. It is sectional drawing which shows an example of a structure of the semiconductor device in this embodiment. It is sectional drawing which shows an example of a structure of the semiconductor device in this embodiment.

  Embodiments of the present invention will be described below with reference to the drawings. In all the drawings, similar constituent elements are denoted by common reference numerals, and description thereof is omitted as appropriate. Moreover, the figure is a schematic diagram and does not match the actual dimensional ratio. In addition, "-" between the numbers in a sentence represents the following from the above, unless there is particular notice.

  The printed wiring board resin composition (P) of the present embodiment (hereinafter also referred to as a resin composition (P)) is a thermosetting resin composition used for forming an insulating layer in a printed wiring board. And a maleimide compound (A). The maleimide compound (A) includes at least a bismaleimide compound (A1) represented by the following formula (a).

（上記式（ａ）において、Ｑは炭素数６以上の２価の直鎖状、分枝鎖状または環状の脂肪族炭化水素基であり、Ｐは２価の原子または有機基であり、ｎは１以上１０以下の整数である）

(In the above formula (a), Q is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 6 or more carbon atoms, P is a divalent atom or organic group, and n Is an integer from 1 to 10.

According to the study of the present inventors, in the thermosetting resin composition containing the maleimide compound (A), the thermosetting resin contains at least the bismaleimide compound (A1) represented by the above formula (a). It became clear that the hardened | cured material formed using the resin composition had small thermal shrinkage at high temperature. The present inventor has made further studies based on the above findings. As a result, by using such a cured product as an insulating layer in a printed wiring board, it is clarified that a printed wiring board having excellent circuit reliability and high insulation reliability under high temperature and high humidity can be realized. The present invention has been completed.
The insulating layer formed of the resin composition (P) has low thermal shrinkage at high temperatures, and therefore can maintain the adhesion between the insulating layer and the circuit layer even when placed in a situation where the temperature changes drastically for a long time. it can. Therefore, it is considered that the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be improved.
In addition, the insulation layer formed from the resin composition (P) has low thermal shrinkage at high temperatures, reducing the stress generated between the semiconductor element and the printed wiring board even if it is left for a long period of time under severe temperature changes. can do. As a result, in the obtained semiconductor device, it is considered that the positional deviation of the semiconductor element with respect to the printed wiring board can be suppressed, and the connection reliability between the semiconductor element and the printed wiring board can be improved.

  Hereinafter, the resin composition (P), the prepreg, the resin substrate, the metal-clad laminate 200, the printed wiring board 300, and the semiconductor device 400 will be described in detail.

  The maleimide compound (A) includes at least a bismaleimide compound (A1) represented by the following formula (a).

（上記式（ａ）において、Ｑは炭素数６以上の２価の直鎖状、分枝鎖状または環状の脂肪族炭化水素基であり、Ｐは２価の原子または有機基であり、ｎは１以上１０以下の整数である）

(In the above formula (a), Q is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 6 or more carbon atoms, P is a divalent atom or organic group, and n Is an integer from 1 to 10.

Here, examples of the divalent atom represented by P include O and S. The divalent organic group includes a group represented by “—CO—”, a group represented by “—COO—”, a group represented by “—CH ₂ —”, and “—C (CH ₃ ) ₂ —. , A group represented by “—C (CF ₃ ) ₂ —”, a group represented by “—S ₂ —”, a group represented by “—SO—”, “—SO ₂ ”. Group represented by-"and the like. Moreover, the organic group containing at least 1 or more of these atoms or organic groups is mentioned. Examples of the organic group including the above-described atom or organic group include those having a hydrocarbon group having 1 to 3 carbon atoms, a benzene ring, a cyclo ring, a urethane bond and the like as a structure other than the above. Examples of P in that case include groups represented by the following chemical formula.

  Specific examples of such a bismaleimide compound (A1) include, for example, a bismaleimide compound represented by the following formula (a1), a bismaleimide compound represented by the following formula (a2), and the following formula (a3). The bismaleimide compound shown etc. are mentioned. Specific examples of the bismaleimide compound represented by the formula (a1) include BMI-1500 (manufactured by Designa Molecules Co., Ltd., molecular weight 1500). Specific examples of the bismaleimide compound represented by the formula (a2) include BMI-1700 (manufactured by Designer Molecules, molecular weight 1700), BMI-1400 (manufactured by Diginer Molecules, molecular weight 1400), and the like. It is done. Specific examples of the bismaleimide compound represented by the formula (a3) include BMI-3000 (manufactured by Designa Molecules Co., Ltd., molecular weight 3000).

上記式（ａ１）において、ｎは１以上１０以下の整数を示す。

In the above formula (a1), n represents an integer of 1 or more and 10 or less.

上記式（ａ２）において、ｎは１以上１０以下の整数を示す。

In the above formula (a2), n represents an integer of 1 or more and 10 or less.

上記式（ａ３）において、ｎは１以上１０以下の整数を示す。

In the above formula (a3), n represents an integer of 1 or more and 10 or less.

  The content of the maleimide compound (A) contained in the resin composition (P) is not particularly limited, but when the total solid content of the resin composition (P) (that is, the component excluding the solvent) is 100% by mass 1.0 mass% or more and 25.0 mass% or less is preferable, 2.0 mass% or more and 22.0 mass% or less are more preferable, and 5.0 mass% or more and 20.0 mass% or less are more preferable. When the content of the maleimide compound (A) is within the above range, the balance between low heat shrinkage and chemical resistance of the cured product of the prepreg and the resin substrate obtained can be further improved.

  The content of the bismaleimide compound (A1) contained in the maleimide compound (A) is not particularly limited, but is 1 mass when the maleimide compound (A) contained in the resin composition (P) is 100 mass%. % To 100% by mass, more preferably 1% to 95% by mass, still more preferably 10% to 75% by mass, and particularly preferably 30% to 75% by mass. When the content of the bismaleimide compound (A1) is within the above range, the balance of low heat shrinkage and chemical resistance of the cured product of the prepreg obtained and the resin substrate can be further improved.

  Although the minimum of the weight average molecular weight (Mw) of a maleimide compound (A) is not specifically limited, Mw400 or more is preferable and especially Mw800 or more is preferable. It can suppress that tackiness arises in a prepreg as Mw is more than the said lower limit. The upper limit of Mw is not particularly limited, but is preferably Mw 4000 or less, and more preferably Mw 2500 or less. When the Mw is not more than the above upper limit value, the impregnation property to the fiber base material is improved during the production of the resin substrate, and a more uniform resin substrate can be obtained. Mw of the maleimide compound (A) can be measured, for example, by GPC (gel permeation chromatography, standard substance: converted to polystyrene).

The resin composition (P) can further contain a different type of maleimide compound (A2) from the bismaleimide compound (A1).
Examples of such maleimide compound (A2) include a maleimide compound represented by the following formula (1); 1,6′-bismaleimide- (2,2,4-trimethyl) hexane, hexamethylenediamine bismaleimide, N , N′-1,2-ethylene bismaleimide, N, N′-1,3-propylene bismaleimide, aliphatic bismaleimide compounds such as N, N′-1,4-tetramethylene bismaleimide, and the like. it can. Among these, a maleimide compound represented by the following formula (1) and 1,6′-bismaleimide- (2,2,4-trimethyl) hexane are particularly preferable. A maleimide compound (A2) may be used independently and may use 2 or more types together.

（式（１）において、ｎ_１は０以上１０以下の整数であり、Ｘ_１はそれぞれ独立に炭素数１以上１０以下のアルキレン基、下記式（１ａ）で表される基、式「−ＳＯ_２−」で表される基、「−ＣＯ−」で表される基、酸素原子または単結合であり、Ｒ_１はそれぞれ独立に炭素数１以上６以下の炭化水素基であり、ａはそれぞれ独立に０以上４以下の整数であり、ｂはそれぞれ独立に０以上３以下の整数である）

(In Formula (1), n ₁ is an integer of 0 or more and 10 or less, X ₁ is independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following Formula (1a), a formula “—SO A group represented by “ _2- ”, a group represented by “—CO—”, an oxygen atom or a single bond, each R ₁ is independently a hydrocarbon group having 1 to 6 carbon atoms, and a is each Each independently represents an integer of 0 or more and 4 or less, and each b is independently an integer of 0 or more and 3 or less)

（上記式（１ａ）において、Ｙは芳香族環を有する炭素数６以上３０以下の炭化水素基であり、ｎ_２は０以上の整数である）

(In the above formula (1a), Y is a hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring, and n ₂ is an integer of 0 or more)

The alkylene group of 1 to 10 in X ₁ is not particularly limited, but is preferably a linear or branched alkylene group.

  Specific examples of the linear alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decanylene group, trimethylene group, tetramethylene group. Group, pentamethylene group, hexamethylene group and the like.

Specific examples of the branched alkylene group include —C (CH ₃ ) ₂ — (isopropylene group), —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, and —C. _{(CH 3) (CH 2 CH} 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - alkyl methylene groups such as; -CH (CH _{3 ) CH 2 -, - CH (} CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH 3) 2 Examples thereof include an alkylethylene group such as —CH ₂ —.

Note that the number of carbon atoms of the alkylene group in X ₁ may be 1 or more and 10 or less, preferably 1 or more and 7 or less, and more preferably 1 or more and 3 or less. Specifically, examples of the alkylene group having such a carbon number include a methylene group, an ethylene group, a propylene group, and an isopropylene group.

R ₁ is independently a hydrocarbon group having 1 to 6 carbon atoms, and is a hydrocarbon group having 1 or 2 carbon atoms, specifically, for example, a methyl group or an ethyl group. Is preferred.

  Furthermore, a is an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 2 or less, and more preferably 0. Further, b is an integer of 0 or more and 3 or less, preferably 0 or 1, and more preferably 0.

N ₁ is an integer of 0 or more and 10 or less, preferably an integer of 0 or more and 6 or less, more preferably an integer of 0 or more and 4 or less, and particularly preferably an integer of 0 or more and 3 or less. preferable. The maleimide compound (A2) more preferably includes at least a compound in which n ₁ is 1 or more in the above formula (1). Thereby, the insulating layer obtained from the resin composition (P) exhibits more excellent heat resistance.
Further, in the above formula (1a), Y is 30 or less hydrocarbon group having 6 or more carbon atoms having an aromatic ring, n ₂ is an integer of 0 or more.

  The hydrocarbon group having 6 to 30 carbon atoms and having an aromatic ring may be composed only of an aromatic ring or may have a hydrocarbon group other than the aromatic ring. Y may have one aromatic ring or two or more aromatic rings, and in the case of two or more, these aromatic rings may be the same or different. The aromatic ring may be a monocyclic structure or a polycyclic structure.

  Specifically, examples of the hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring include aromatics such as benzene, biphenyl, naphthalene, anthracene, fluorene, phenanthrene, indacene, terphenyl, acenaphthylene, and phenalene. And a divalent group obtained by removing two hydrogen atoms from the nucleus of a compound having family properties.

  Moreover, these aromatic hydrocarbon groups may have a substituent. Here, that the aromatic hydrocarbon group has a substituent means that part or all of the hydrogen atoms constituting the aromatic hydrocarbon group are substituted by the substituent. Examples of the substituent include an alkyl group.

  The alkyl group as the substituent is preferably a chain alkyl group. The number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, and a sec-butyl group.

  Such a group Y preferably has a group obtained by removing two hydrogen atoms from benzene or naphthalene. Examples of the group represented by the above formula (1a) include the following formulas (1a-1) and (1a-2). It is preferable that it is group represented by either of these. Thereby, the insulating layer obtained from the resin composition (P) exhibits more excellent heat resistance.

上記式（１ａ−１）、（１ａ−２）中、Ｒ_４は、それぞれ独立に炭素数１以上６以下の炭化水素基である。ｅはそれぞれ独立に０以上４以下の整数、より好ましくは０である。

In the above formulas (1a-1) and (1a-2), R ₄ is each independently a hydrocarbon group having 1 to 6 carbon atoms. Each e is independently an integer of 0 or more and 4 or less, more preferably 0.

Further, in the group represented by the above formula (1a), n ₂ may be an integer of 0 or more, preferably an integer of 0 or more and 5 or less, and preferably an integer of 1 or more and 3 or less. More preferably, 1 or 2 is particularly preferable.

From the above, in the maleimide compound (A2) represented by the above formula (1), X ₁ is a linear or branched alkylene group having 1 to 3 carbon atoms, and R ₁ is 1 or 2 It is preferable that a is an integer of 0 or more and 2 or less, b is 0 or 1, and n ₁ is an integer of 1 or more and 4 or less. Alternatively, X ₁ is a group represented by any _one of the above formulas (1a-1) and (1a-2), and e is preferably 0. Thereby, the insulating layer obtained from the resin composition (P) exhibits more excellent low heat shrinkability and chemical resistance.

  As a preferable specific example of the maleimide compound (A2) represented by the above formula (1), for example, a maleimide compound represented by the following formula (1-1) is particularly preferably used.

  The resin composition (P) preferably further contains a benzoxazine compound (B) from the viewpoint of further improving the cured product of the obtained prepreg and the low thermal shrinkage and chemical resistance of the resin substrate. The benzoxazine compound (B) is a compound having a benzoxazine ring. Examples of the benzoxazine compound (B) include one or more selected from a compound represented by the following formula (2) and a compound represented by the following formula (3).

（上記式（２）において、Ｘ_２はそれぞれ独立に炭素数１以上１０以下のアルキレン基、上記式（１ａ）で表される基、式「−ＳＯ_２−」で表される基、「−ＣＯ−」で表される基、酸素原子または単結合であり、Ｒ_２はそれぞれ独立に炭素数１以上６以下の炭化水素基であり、ｃはそれぞれ独立に０以上４以下の整数である）

(In the above formula (2), each X ₂ independently represents an alkylene group having 1 to 10 carbon atoms, a group represented by the above formula (1a), a group represented by the formula “—SO ₂ —”, “— A group represented by “CO—”, an oxygen atom or a single bond, R ₂ is each independently a hydrocarbon group having 1 to 6 carbon atoms, and c is each independently an integer of 0 to 4)

（上記式（３）において、Ｘ_３はそれぞれ独立に炭素数１以上１０以下のアルキレン基、上記式（１ａ）で表される基、式「−ＳＯ_２−」で表される基、「−ＣＯ−」で表される基、酸素原子または単結合であり、Ｒ_３はそれぞれ独立に炭素数１以上６以下の炭化水素基であり、ｄはそれぞれ独立に０以上４以下の整数である）

(In the formula (3), X ₃ each independently represents an alkylene group having 1 to 10 carbon atoms, a group represented by the formula (1a), a group represented by the formula “—SO ₂ —”, “— A group represented by "CO-", an oxygen atom or a single bond, each R ₃ is independently a hydrocarbon group having 1 to 6 carbon atoms, and d is each independently an integer of 0 to 4)

Examples of X ₂ and X ₃ in the above formula (2) and the above formula (3) include the same as those described for X ₁ in the above formula (1). In addition, R ₂ and R ₃ in the above formula (2) and the above formula (3) can be the same as those described for R ₁ in the above formula (1). Furthermore, the above formula (2) and C and d in the above formula (3) can be the same as those described for a in the above formula (1).

  The benzoxazine compound (B) is a compound represented by the above formula (2) among the compounds represented by the above formula (2) and the above formula (3). preferable. Thereby, the insulating layer obtained from the resin composition (P) exhibits more excellent low heat shrinkability and chemical resistance.

In the compound represented by the formula (2), X ₂ is a linear or branched alkylene group having 1 to 3 carbon atoms, and R ₂ is a hydrocarbon group having 1 or 2 carbon atoms. And c is preferably an integer of 0 or more and 2 or less. Alternatively, X ₂ is a group represented by any one of the formulas (1a-1) and (1a-2), and c is preferably 0. Thereby, the insulating layer obtained from the resin composition (P) exhibits more excellent low heat shrinkability and chemical resistance.

  Preferred specific examples of the benzoxazine compound (B) include, for example, a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), and a compound represented by the following formula (2-3). , One or more selected from compounds represented by the following formula (3-1), compounds represented by the following formula (3-2), and compounds represented by the following formula (3-3).

（上記式（２−３）において、Ｒはそれぞれ独立に炭素数１〜４の炭化水素基である）

(In the above formula (2-3), each R is independently a hydrocarbon group having 1 to 4 carbon atoms)

  The content of the benzoxazine compound (B) contained in the resin composition (P) is not particularly limited, but the total solid content (that is, the component excluding the solvent) of the resin composition (P) is 100% by mass. In this case, 1.0% by mass to 25.0% by mass is preferable, and 2.0% by mass to 15.0% by mass is more preferable. When the content of the benzoxazine compound (B) is within the above range, the cured product of the obtained prepreg and the low thermal shrinkage and chemical resistance of the resin substrate can be further improved.

  The content of the maleimide compound (A) contained in the resin composition (P) is 35% by mass or more and 80% by mass or less with respect to 100% by mass in total of the maleimide compound (A) and the benzoxazine compound (B). It is preferable. Thereby, the heat resistance of the hardened | cured material of the obtained prepreg and a resin substrate, low heat shrinkability, and chemical resistance can be improved further.

The resin composition (P) according to the present embodiment can further include an epoxy resin (D).
Examples of the epoxy resin (D) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4 ′-(1,3- Phenylenediisopridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4 '-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4' Bisphenol-type epoxy resins such as cyclohexenediene bisphenol-type epoxy resins; phenol novolak-type epoxy resins, cresol novolak-type epoxy resins, tetraphenol-based ethane-type novolak-type epoxy resins, and noses having a condensed ring aromatic hydrocarbon structure Novolak type epoxy resins such as rack type epoxy resins; biphenyl type epoxy resins; aralkyl type epoxy resins such as xylylene type epoxy resins and biphenyl aralkyl type epoxy resins; naphthylene ether type epoxy resins, naphthol type epoxy resins, naphthalenediol type epoxy resins Naphthalene type epoxy resins such as bifunctional to tetrafunctional epoxy type naphthalene resins, binaphthyl type epoxy resins, naphthalene aralkyl type epoxy resins; anthracene type epoxy resins; phenoxy type epoxy resins; dicyclopentadiene type epoxy resins; norbornene type epoxy resins; Examples thereof include adamantane type epoxy resins; fluorene type epoxy resins.

  As the epoxy resin (D), one of these may be used alone, two or more of them may be used in combination, and one or two or more thereof and a prepolymer thereof may be used in combination. .

  Among epoxy resins (D), bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthalene type from the viewpoint of further improving the heat resistance and insulation reliability of the obtained printed wiring board One or more selected from the group consisting of epoxy resins, anthracene type epoxy resins and dicyclopentadiene type epoxy resins are preferred, aralkyl type epoxy resins, novolak type epoxy resins having a condensed ring aromatic hydrocarbon structure and naphthalene types One or more selected from the group consisting of epoxy resins are more preferred.

  As the bisphenol A type epoxy resin, "Epicoat 828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation can be used. As the bisphenol F type epoxy resin, “jER806H” and “YL983U” manufactured by Mitsubishi Chemical Corporation, “EPICLON 830S” manufactured by DIC Corporation, and the like can be used. As the bifunctional naphthalene type epoxy resin, “HP4032”, “HP4032D”, “HP4032SS” manufactured by DIC, and the like can be used. As the tetrafunctional naphthalene type epoxy resin, “HP4700” and “HP4710” manufactured by DIC, etc. can be used. As the naphthol type epoxy resin, “ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd., “NC7000L” manufactured by Nippon Kayaku Co., Ltd. and the like can be used. As the aralkyl type epoxy resin, “NC3000”, “NC3000H”, “NC3000L”, “NC3000S”, “NC3000S-H”, “NC3100” manufactured by Nippon Kayaku Co., Ltd., “ESN-170” manufactured by Nippon Steel Chemical Co., Ltd. And “ESN-480” can be used. As the biphenyl type epoxy resin, “YX4000”, “YX4000H”, “YX4000HK”, “YL6121”, etc. manufactured by Mitsubishi Chemical Corporation can be used. As the anthracene type epoxy resin, “YX8800” manufactured by Mitsubishi Chemical Corporation can be used. As the naphthylene ether type epoxy resin, “HP6000”, “EXA-7310”, “EXA-7311”, “EXA-7311L”, “EXA7311-G3” and the like manufactured by DIC can be used.

  As the epoxy resin (D), one of these may be used alone, two or more may be used in combination, or one or two or more and those prepolymers may be used in combination. Good.

  Among these epoxy resins (D), an aralkyl type epoxy resin is particularly preferable. Thereby, the moisture absorption solder heat resistance and flame retardance of the resin substrate can be further improved.

  Although the minimum of the weight average molecular weight (Mw) of an epoxy resin (D) is not specifically limited, Mw300 or more is preferable and especially Mw800 or more is preferable. It can suppress that tackiness arises in a prepreg as Mw is more than the said lower limit. The upper limit of Mw is not particularly limited, but is preferably Mw 20,000 or less, and particularly preferably Mw 15,000 or less. When the Mw is not more than the above upper limit, the impregnation property to the fiber base material is improved at the time of producing the prepreg, and a more uniform prepreg can be obtained. The Mw of the epoxy resin can be measured by GPC, for example.

  The content of the epoxy resin (D) contained in the resin composition (P) is not particularly limited as long as it is appropriately adjusted according to the purpose, but the inorganic filler (C) in the resin composition (P). When the total amount of the components excluding is 100% by mass, it is preferably 1% by mass or more and 50% by mass or less. When the content of the epoxy resin (D) is not less than the above lower limit value, handling properties are improved, and it becomes easy to form a prepreg. When the content of the epoxy resin (D) is less than or equal to the above upper limit, the strength and flame retardancy of the obtained printed wiring board are improved, the linear expansion coefficient of the printed wiring board is lowered, and the warp reduction effect is improved. There is a case to do.

  It is preferable that the resin composition (P) according to the present embodiment further includes an inorganic filler (C). Thereby, the hardened | cured material of the obtained prepreg and the storage elastic modulus E 'of a resin substrate can be improved. Furthermore, the linear expansion coefficient of the insulating layer 301 obtained can be reduced.

Examples of the inorganic filler (C) include silicates such as talc, fired clay, unfired clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, silica, and fused silica; calcium carbonate and magnesium carbonate Carbonates such as hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite; zinc borate, barium metaborate, Borates such as aluminum borate, calcium borate and sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride and carbon nitride; titanates such as strontium titanate and barium titanate it can.
Among these, talc, alumina, glass, silica, mica, boehmite, aluminum hydroxide, and magnesium hydroxide are preferable, and silica is particularly preferable. As the inorganic filler (C), one of these may be used alone, or two or more may be used in combination.

Although the average particle diameter of an inorganic filler (C) is not specifically limited, 0.01 micrometer or more is preferable and 0.05 micrometer or more is more preferable. When the average particle diameter of the inorganic filler (C) is not less than the above lower limit value, it is possible to suppress the viscosity of the varnish from being increased, and the workability at the time of producing the prepreg can be improved. The average particle diameter of the inorganic filler (C) is not particularly limited, but is preferably 5.0 μm or less, more preferably 2.0 μm or less, and further preferably 1.0 μm or less. When the average particle size of the inorganic filler (C) is not more than the above upper limit value, phenomena such as sedimentation of the inorganic filler (C) in the varnish can be suppressed, and a more uniform resin layer can be obtained. Further, when the circuit dimension L / S of the printed wiring board is less than 20/20 μm, it is possible to suppress the influence on the insulation between the wirings.
The average particle size of the inorganic filler (C) is measured, for example, by measuring the particle size distribution on a volume basis using a laser diffraction particle size distribution measuring device (LA-500, manufactured by HORIBA), and the median diameter (D ₅₀ ). Can be the average particle size.

  The inorganic filler (C) is not particularly limited, but an inorganic filler having a monodispersed average particle diameter may be used, or an inorganic filler having a polydispersed average particle diameter may be used. Furthermore, one type or two or more types of inorganic fillers having a monodispersed and / or polydispersed average particle size may be used in combination.

  The inorganic filler (C) is preferably silica particles, preferably silica particles having an average particle size of 5.0 μm or less, more preferably silica particles having an average particle size of 0.1 μm to 4.0 μm, and 0.2 μm to 2.0 μm. The following silica particles are particularly preferred. Thereby, the filling property of an inorganic filler (C) can further be improved.

  The content of the inorganic filler (C) contained in the resin composition (P) is not particularly limited, but the total solid content (that is, the component excluding the solvent) of the resin composition (P) is 100% by mass. When it is 50.0 mass% or more and 85.0 mass% or less, 60.0 mass% or more and 80.0 mass% or less are more preferable. When the content of the inorganic filler (C) is within the above range, the obtained prepreg cured product or resin substrate can be further reduced in thermal expansion and water absorption.

It is preferable that the resin composition (P) further includes a low stress material (E). Thereby, the cured product of the obtained prepreg and the stress of the resin substrate can be relaxed, and the adhesion with other members such as a circuit layer can be further improved.
Examples of the low stress material (E) include (meth) acrylic block copolymer; silicone compound; acrylonitrile-butadiene rubber modified with carboxyl group, amino group, vinyl acrylate group or epoxy group; aliphatic epoxy resin; And one or more selected from rubber particles and the like.

  The (meth) acrylic block copolymer is a block copolymer containing a (meth) acrylic monomer as an essential monomer component. Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methacrylic acid. (Meth) acrylic acid alkyl esters such as t-butyl acid, 2-ethylhexyl methacrylate, lauryl methacrylate and stearyl methacrylate; (meth) acrylic acid esters having an alicyclic structure such as cyclohexyl acrylate and cyclohexyl methacrylate; methacryl (Meth) acrylic acid ester having an aromatic ring such as benzyl acid; (fluoro) alkyl ester of (meth) acrylic acid such as 2-trifluoroethyl methacrylate; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, etc. Min A carboxyl group-containing acrylic monomer having a carboxyl group therein; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacryl Hydroxyl group-containing acrylic monomer having hydroxyl group in molecule such as 4-hydroxybutyl acid, mono (meth) acrylic acid ester of glycerin; molecule such as glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate An acrylic monomer having an epoxy group therein; an allyl group-containing acrylic monomer having an allyl group in a molecule such as allyl acrylate and allyl methacrylate; γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyl Silane group-containing acrylic monomer having hydrolyzable silyl group in the molecule such as oxypropyltriethoxysilane; benzotriazole such as 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole And UV-absorbing acrylic monomers having a UV-absorbing group.

  In the (meth) acrylic block copolymer, a monomer other than the acrylic monomer may be used as a monomer component. Examples of the monomer other than the acrylic monomer include aromatic vinyl compounds such as styrene and α-methylstyrene, conjugated dienes such as butadiene and isoprene, and olefins such as ethylene, propylene and isobutene.

  Although it does not specifically limit as said (meth) acrylic-type block copolymer, For example, the diblock copolymer which consists of two polymer blocks, the triblock copolymer which consists of three polymer blocks, 4 or more And a multi-block copolymer composed of the polymer block.

  Among them, as the (meth) acrylic block copolymer, from the viewpoint of improving heat resistance, light resistance, and crack resistance, a polymer block (S) (soft block) having a low glass transition temperature (Tg), A block copolymer in which polymer blocks (H) (hard blocks) having a Tg higher than that of the polymer block (S) are alternately arranged is preferred, more preferably a polymer block (S) in the middle, A triblock copolymer having an HSH structure having polymer blocks (H) at both ends is preferred.

  As a preferable specific example of the (meth) acrylic block copolymer in the resin composition (P), for example, the polymer block (S) is a polymer composed of butyl acrylate (BA) as a main monomer, Polymethylmethacrylate-block-polybutylacrylate-block-polymethylmethacrylate terpolymer (PMMA-b-PBA-b), wherein the polymer block (H) is a polymer composed mainly of methyl methacrylate (MMA). -PMMA) and the like.

  Examples of the (meth) acrylic block copolymer include trade names “Nano Strength M52N”, “Nano Strength M22N”, “Nano Strength M51”, “Nano Strength M52”, “Nano Strength M53” (Arkema). Commercial products such as PMMA-b-PBA-b-PMMA), trade names “Nanostrength E21”, “Nanostrength E41” (manufactured by Arkema, PSt (polystyrene) -b-PBA-b-PMMA) It can also be used.

  Examples of the silicone compound include silicone rubber, silicone oil, silicone powder, silicone resin, silicone epoxy resin, amine-modified silicone resin, epoxy group- and phenyl group-containing three-dimensional crosslinked silicone resin, and the like.

  The aliphatic epoxy resin is preferably an aliphatic epoxy resin having no cyclic structure other than the glycidyl group, and more preferably a bifunctional or higher functional aliphatic epoxy resin having two or more glycidyl groups. Such an aliphatic epoxy resin is excellent because an epoxy group is not easily oxidized and an elastic modulus is hardly increased due to thermal history.

  Examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and silicone particles.

  The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is formed of a glassy polymer and an inner core layer is formed of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glassy polymer layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N (trade names, manufactured by Ganz Kasei Co., Ltd.), and Metabrene KW-4426 (trade names, manufactured by Mitsubishi Rayon Co., Ltd.). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size: 0.5 μm, manufactured by JSR).

  Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle size: 0.5 μm, manufactured by JSR). Specific examples of the acrylic rubber particles include methabrene W300A (average particle size 0.1 μm), W450A (average particle size 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.), and the like.

  The silicone particles are not particularly limited as long as they are rubber elastic fine particles formed of organopolysiloxane. For example, fine particles made of silicone rubber (organopolysiloxane crosslinked elastomer) itself and a core portion made of silicone mainly composed of two-dimensional crosslinks. Examples thereof include core-shell structured particles coated with silicone mainly composed of a three-dimensional crosslinking type. As silicone rubber fine particles, commercially available products such as KMP-605, KMP-600, KMP-597, KMP-594 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil E-500, Trefil E-600 (manufactured by Toray Dow Corning), etc. Can be used.

  The content of the low-stress material (E) contained in the resin composition (P) is not particularly limited, but the total solid content of the resin composition (P) (that is, the component excluding the solvent) is 100% by mass. When it is 0.1 mass% or more and 10.0 mass% or less, 1.0 mass% or more and 8.0 mass% or less are more preferable. When the content of the low-stress material (E) is within the above range, the stress of the resulting prepreg cured product and resin substrate can be further relaxed, and the adhesion to other members such as circuit layers can be further improved. You can make it.

  In addition, a curing accelerator and a coupling agent can be appropriately blended in the resin composition (P) as necessary.

  The curing accelerator is not particularly limited, and examples thereof include phosphine compounds, compounds having a phosphonium salt, imidazole compounds, and the like, and one or a combination of two or more of these can be used. Of these, imidazole compounds are preferred. Since the imidazole compound has a particularly excellent function as a catalyst, the polymerization reaction of the maleimide compound (A) can be promoted more reliably.

  The imidazole compound is not particularly limited, and examples thereof include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, and 2-heptadecylimidazole. 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl- 2- Down decyl imidazole, 1-cyanoethyl-2-phenylimidazole and the like, it can be used in combination of one or two or more of these. Among these, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and 2-ethyl-4-methylimidazole are preferable. By using these compounds, the reaction of the maleimide compound (A) is further promoted, and the molding processability is improved and the heat resistance of the obtained cured product is improved.

  Examples of the phosphine compound include primary phosphines such as ethyl phosphine and alkyl phosphine such as propyl phosphine, and phenyl phosphine; Trialkylphosphine such as trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, alkyldiphenylphosphine, dialkylphenylphosphine, tribenzylphosphine, tolylphosphine, tri-p-styrylphosphine , Tris (2,6-dimethoxyphenyl) phosphine, tri-4-methylphenol Le phosphine, tri-4-methoxyphenyl phosphine, tertiary phosphines such as tri-2-cyanoethyl phosphine, and the like. Among these, tertiary phosphine is preferably used.

Examples of the compound having a phosphonium salt include a compound having a tetraphenylphosphonium salt, an alkyltriphenylphosphonium salt, and the like. Specifically, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium tetra-p-methylphenylborate, butyl Examples include triphenylphosphonium thiocyanate.

  The content of the curing accelerator is preferably 0.01 to 5.0 parts by mass, more preferably 0.05 to 3.0 parts by mass with respect to 100 parts by mass of the maleimide compound (A). It is especially preferable that it is 0.1-1.5 mass parts. By setting content of a hardening accelerator in this range, the heat resistance of the hardened | cured material obtained from a resin composition (P) can be made more excellent.

  Furthermore, the resin composition (P) may contain a coupling agent. The coupling agent may be added directly at the time of preparing the resin composition (P), or may be added in advance to the inorganic filler (C). By using the coupling agent, the wettability of the interface between the fiber substrate or the inorganic filler (C) and each resin can be improved. Therefore, it is preferable to use a coupling agent, and the heat resistance of the obtained prepreg cured product or resin substrate can be improved.

Examples of the coupling agent include silane coupling agents such as epoxy silane coupling agents, cationic silane coupling agents, and amino silane coupling agents, titanate coupling agents, and silicone oil type coupling agents. A coupling agent may be used individually by 1 type, and may use 2 or more types together.
Thereby, the wettability of the interface of a fiber base material or an inorganic filler (C) and each resin can be made high, and the heat resistance of the hardened | cured material of a prepreg obtained or a resin substrate can be improved more.

  Various types of silane coupling agents can be used, and examples thereof include epoxy silane, amino silane, alkyl silane, ureido silane, mercapto silane, and vinyl silane.

  Specific examples of the compound include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-amino. Propylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (aminohexyl) 3-aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldimethoxysilane, β- (3,4 Poxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, γ-ureidopropyltriethoxysilane, vinyltriethoxysilane, etc., and a combination of one or more of these. Of these, epoxy silane, mercapto silane, and amino silane are preferable, and as amino silane, primary amino silane or anilide silane is more preferable.

The addition amount of the coupling agent is not particularly limited because it depends on the specific surface area of the inorganic filler (C), but the total solid content (that is, the component excluding the solvent) of the resin composition (P) is 100% by mass. When it is 0.01 mass% or more and 1 mass% or less, 0.05 mass% or more and 0.5 mass% or less are more preferable.
When the content of the coupling agent is not less than the above lower limit value, the inorganic filler (C) can be sufficiently covered, and the obtained prepreg cured product and the heat resistance of the resin substrate can be improved. Moreover, it can suppress that reaction influences that content of a coupling agent is below the said upper limit, and can suppress the fall of the bending strength of the hardened | cured material of a prepreg obtained, or a resin substrate.

  Furthermore, the resin composition (P) has pigments, dyes, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, ion scavengers and the like as long as the object of the present invention is not impaired. Additives other than the above components may be added.

  Examples of pigments include kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, strontium yellow, hydrous chromium oxide, chromium oxide, cobalt aluminate, synthetic ultramarine blue, etc., polycyclic pigments such as phthalocyanine, azo pigments Etc.

  Examples of the dye include isoindolinone, isoindoline, quinophthalone, xanthene, diketopyrrolopyrrole, perylene, perinone, anthraquinone, indigoid, oxazine, quinacridone, benzimidazolone, violanthrone, phthalocyanine, azomethine and the like.

Resin composition (P) is acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol, In organic solvents such as anisole and N-methylpyrrolidone, using various mixing machines such as ultrasonic dispersion method, high-pressure collision dispersion method, high-speed rotation dispersion method, bead mill method, high-speed shear dispersion method, rotation and revolution dispersion method, etc. The resin varnish (I) can be obtained by dissolving, mixing and stirring.
The solid content of the resin varnish (I) is not particularly limited, but is preferably 40% by mass or more and 80% by mass or less, and particularly preferably 50% by mass or more and 70% by mass or less. Thereby, the impregnation property to the fiber base material of resin varnish (I) can further be improved.

In the above resin composition (P), the ratio of each component is as follows, for example.
When the total solid content of the resin composition (P) (that is, the component excluding the solvent) is 100% by mass, the ratio of the maleimide compound (A) is preferably 1.0% by mass or more and 25.0% by mass or less. Yes, the proportion of the benzoxazine compound (B) is 1.0% by mass or more and 25.0% by mass or less, and the proportion of the inorganic filler (C) is 50.0% by mass or more and 85.0% by mass or less.
More preferably, the ratio of the maleimide compound (A) is 5.0% by mass or more and 20.0% by mass or less, and the ratio of the benzoxazine compound (B) is 2.0% by mass or more and 15.0% by mass or less. The ratio of the inorganic filler (C) is 60.0% by mass or more and 80.0% by mass or less.

  Next, the prepreg in the present embodiment will be described.

  The prepreg is used for forming an insulating layer of a printed wiring board. The prepreg is, for example, a sheet-like material obtained by impregnating the fiber base material with the resin composition (P) in the present embodiment and then semi-curing it.

The resin substrate is used for forming an insulating layer of the printed wiring board.
Here, the resin substrate contains a cured product of prepreg, and can be obtained, for example, by heat-curing the prepreg.

The prepreg can be used, for example, to form an insulating layer in a buildup layer or an insulating layer in a core layer in a printed wiring board.
When the prepreg is used to form an insulating layer in the core layer of the printed wiring board, for example, two or more prepregs are stacked, and the obtained laminate is heat-cured to form an insulating layer for the core layer. You can also.

Further, from the viewpoint of improving the rigidity and heat resistance of a printed wiring board obtained using the prepreg, a prepreg measured by dynamic viscoelasticity measurement under conditions of a temperature rising rate of 5 ° C./min and a frequency of 1 Hz, for example, The glass transition temperature of a cured product or resin substrate obtained by heat-press molding at a pressure of 4 MPa and a temperature of 230 ° C. for 2 hours is preferably 250 ° C. or higher, more preferably 260 ° C. or higher, and further preferably 270. It is at least 280 ° C, particularly preferably at least 280 ° C. About an upper limit, 400 degrees C or less is preferable, for example. The glass transition temperature can be measured using a dynamic viscoelasticity analyzer (DMA).
Moreover, in the said hardened | cured material or resin board | substrate, when the glass transition temperature by dynamic viscoelasticity measurement satisfy | fills the said range, the rigidity of the obtained printed wiring board will increase and the curvature of the printed wiring board at the time of mounting can be reduced further. As a result, in the obtained semiconductor device, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability between the semiconductor element and the printed wiring board can be further enhanced.
In order to achieve such a glass transition temperature, maleimide compound (A), benzoxazine compound (B), inorganic filler (C), epoxy resin (D), low stress material (E), fiber substrate, It is important to appropriately control the type and blending amount of the curing accelerator, the prepreg production method, and the like.

In addition, from the viewpoint of further improving the balance of rigidity, heat resistance, and stress relaxation ability of the printed wiring board obtained using the prepreg, the prepreg is heated and pressed at a pressure of 4 MPa and a temperature of 230 ° C. for 2 hours, for example. The obtained cured product or resin substrate has a storage elastic modulus E ′ ₃₀ at 30 ° C. of preferably 10 GPa or more, and more preferably 20 GPa or more. Although it does not specifically limit about an upper limit, For example, it can be 40 GPa or less.
When the storage elastic modulus E ′ ₃₀ at 30 ° C. satisfies the above range in the cured product or resin substrate, the performance balance of rigidity, heat resistance, and stress relaxation ability of the obtained printed wiring board is improved, and printing at the time of mounting is performed. The warping of the wiring board can be further reduced. As a result, in the obtained semiconductor device, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability between the semiconductor element and the printed wiring board can be further enhanced.

In addition, from the viewpoint of further improving the balance of rigidity, heat resistance, and stress relaxation ability of the printed wiring board obtained using the prepreg, the prepreg is heated and pressed at a pressure of 4 MPa and a temperature of 230 ° C. for 2 hours, for example. The ratio (E ′ ₃₀ / E ′ ₂₅₀ ) of the storage elastic modulus E ′ ₃₀ at 30 ° C. to the storage elastic modulus E ′ ₂₅₀ at 250 ° C. of the obtained cured product or resin substrate is 1.05 or more and 1.75 or less. It is preferable that
In the cured product or a resin substrate, when _{E '30 /} E' ₂₅₀ satisfies the above range, can be further suppress a change in the elastic modulus of the printed wiring board to a temperature change. As a result, even when a large temperature change occurs, the insulating layer is not easily deformed, the positional deviation of the semiconductor element relative to the printed wiring board can be suppressed, and the connection reliability between the semiconductor element and the printed wiring board is further improved. Can do.

In order to achieve such storage elastic modulus E ′ ₃₀ and E ′ ₃₀ / E ′ ₂₅₀ , maleimide compound (A), benzoxazine compound (B), inorganic filler (C), epoxy resin (D), It is important to appropriately control the types and blending amounts of the low-stress material (E), the fiber base material, the curing accelerator, the prepreg production method, and the like.

Further, from the viewpoint of further improving the insulation reliability of the printed wiring board under high temperature and high humidity and the connection reliability between the semiconductor element and the printed wiring board, the prepreg is, for example, 2 at a pressure of 4 MPa and a temperature of 230 ° C. in the in-plane direction of the cured product or a resin substrate obtained by molding time heating and pressurizing, it is preferably the average linear expansion coefficient alpha ₁ calculated in the range of 0.99 ° C. from 50 ° C. or less 7.5 ppm / ° C., more preferably Is 7.2 ppm / ° C. or less, and particularly preferably 6.0 ppm / ° C. or less. Although it does not specifically limit about a lower limit, For example, it can be set as 0.1 ppm / degrees C or more.
In the cured product or resin substrate, the average coefficient of linear expansion alpha ₁ satisfies the above range, the printed wiring board obtained, even if a large change in environmental temperature, linear expansion coefficient between the circuit layer and the insulating layer The stress generated due to the difference can be further reduced. Therefore, in the obtained printed wiring board and semiconductor device, the adhesion between the circuit layer and the insulating layer can be maintained even when the temperature change is severe for a long period of time. Thereby, the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be further enhanced.
In the cured product or resin substrate, the average coefficient of linear expansion alpha ₁ satisfies the above range, the semiconductor device obtained, when exposed to a high temperature in the linear expansion coefficient difference between the printed circuit board and the semiconductor element The stress generated due to this can be reduced. As a result, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability at high temperatures and the temperature cycle reliability between the semiconductor element and the printed wiring board can be further enhanced.

Further, from the viewpoint of further improving the insulation reliability of the printed wiring board under high temperature and high humidity and the connection reliability between the semiconductor element and the printed wiring board, the prepreg is, for example, 2 at a pressure of 4 MPa and a temperature of 230 ° C. Average linear expansion calculated in the range of 150 ° C. to 250 ° C. with respect to the average linear expansion coefficient α ₁ calculated in the range of 50 ° C. to 150 ° C. in the in-plane direction of the cured product or resin substrate obtained by time heating and pressing. The ratio of the coefficient α ₂ (α ₂ / α ₁ ) is preferably 0.7 or more and 2.0 or less, more preferably 0.75 or more and 1.5 or less, and further preferably 0.8 or more and 1.2 or less.
In the present embodiment, the average linear expansion coefficients α ₁ and α ₂ are a temperature range of 30 ° C. to 260 ° C. and a temperature increase rate of 10 using a TMA (thermomechanical analysis) apparatus (TA Instruments, Q400). It is the average value of the coefficient of linear expansion (CTE) in the plane direction (XY direction) measured under the conditions of ° C./min, load 10 g, and compression mode.
When α ₂ / α ₁ satisfies the above range in the cured product or the resin substrate, even if a large change occurs in the environmental temperature in the obtained printed wiring board, the difference in linear expansion coefficient between the circuit layer and the insulating layer It is possible to reduce a change in stress caused by the above. Therefore, in the obtained printed wiring board and semiconductor device, the adhesion between the circuit layer and the insulating layer can be maintained even when the temperature change is severe for a long period of time. From the above, by using the prepreg, the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be further improved.
Furthermore, when α ₂ / α ₁ satisfies the above range in the cured product or the resin substrate, even if a large change occurs in the environmental temperature in the obtained semiconductor device, the linear expansion between the printed wiring board and the semiconductor element It is possible to reduce a change in stress caused by the coefficient difference. As a result, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability at high temperatures and the temperature cycle reliability between the semiconductor element and the printed wiring board can be further enhanced.

Also, from the viewpoint of improving the insulation reliability of the printed wiring board under high temperature and high humidity and the connection reliability between the semiconductor element and the printed wiring board, the prepreg is heated at a pressure of 4 MPa and a temperature of 230 ° C. for 2 hours, for example. in the in-plane direction of the cured product or a resin substrate obtained by molding under pressure, it is preferably the average linear expansion coefficient alpha ₂ calculated in a range of 250 ° C. from 0.99 ° C. or less 8.0 ppm / ° C., more preferably 7 0.5 ppm / ° C. or less, particularly preferably 6.5 ppm / ° C. or less. Although it does not specifically limit about a lower limit, For example, it can be set as 0.1 ppm / degrees C or more.
Line between the above cured product or resin substrate, the average coefficient of linear expansion alpha ₂ satisfies the above range, the printed wiring board obtained, when exposed to high temperatures of the solder reflow or the like and the circuit layer insulating layer The stress generated due to the difference in expansion coefficient can be reduced. Therefore, in the obtained printed wiring board and semiconductor device, the adhesion between the circuit layer and the insulating layer can be maintained even when the temperature change is severe for a long period of time. Thereby, the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be further enhanced.
The linear expansion coefficient between the above cured product or resin substrate, the average coefficient of linear expansion alpha ₂ satisfies the above range, the semiconductor device obtained, a printed wiring board and the semiconductor element when exposed to high temperatures The stress generated due to the difference can be further reduced. As a result, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability at high temperatures and the temperature cycle reliability between the semiconductor element and the printed wiring board can be further enhanced.

In order to achieve such average linear expansion coefficients α ₁ , α ₂ , α ₂ / α ₁ , maleimide compound (A), benzoxazine compound (B), inorganic filler (C), epoxy resin (D) It is important to appropriately control the kind and blending amount of the low-stress material (E), fiber base material, curing accelerator, etc., the prepreg production method, and the like.

In addition, from the viewpoint of further improving the connection reliability between the semiconductor element and the printed wiring board, for example, in a cured product or a resin substrate obtained by heat-press molding the prepreg at a pressure of 4 MPa and a temperature of 230 ° C. for 2 hours. When using a thermomechanical analyzer, when performing a thermomechanical analysis consisting of a process of raising the temperature from 30 ° C to 260 ° C at 10 ° C / min and a process of maintaining at 260 ° C for 1 hour, reference length of a previous reference length L ₀ of the longitudinal length of the cured product, when the maximum amount of thermal expansion from the reference length L ₀ of the cured product as L _1, where the cured product was held for 1 hour at 260 ° C. When the amount of thermal expansion from L ₀ is L ₂ , the dimensional shrinkage represented by 100 × (L ₁ −L ₂ ) / L ₀ is preferably 0.15% or less, and is 0.10% or less. More preferably. Although it does not specifically limit about a lower limit, For example, it can be 0.00% or more.
In addition, the vertical direction of hardened | cured material points out the conveyance direction (what is called MD) of a prepreg.
When the dimensional shrinkage rate satisfies the above range in the cured product or the resin substrate, the stress generated due to the shrinkage of the insulating layer in the printed wiring board is reduced in the obtained semiconductor device when exposed to a high temperature. can do. As a result, it is possible to maintain the adhesion between the insulating layer and the circuit layer even if the temperature change is severe for a long period of time, so that the insulation reliability of the obtained printed wiring board under high temperature and high humidity is improved. be able to. Further, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability at a high temperature and the temperature cycle reliability between the semiconductor element and the printed wiring board can be further improved.

  In order to achieve such a dimensional shrinkage rate, maleimide compound (A), benzoxazine compound (B), inorganic filler (C), epoxy resin (D), low stress material (E), fiber substrate, It is important to appropriately control the type and blending amount of the curing accelerator, the prepreg production method, and the like.

In addition, from the viewpoint of further improving the cured product of the prepreg or the fine wiring workability of the resin substrate, the cured product obtained by subjecting the prepreg to, for example, heat pressure molding at a pressure of 4 MPa and a temperature of 230 ° C. for 2 hours. When the mass after drying at 120 ° C. for 1 hour is defined as the first mass, and the cured product after the cured product is treated under the following conditions, the mass after drying at 120 ° C. for 1 hour is defined as the second mass. {(First mass)-(second mass)} / (sum of the areas of the front and back surfaces of the cured product)] × 100 The film reduction amount defined by 100 is 1.2 g / m ² or less. preferable.
<Conditions>
The cured product is immersed in a 3 g / L sodium hydroxide solution (solvent: 11.1% by volume of diethylene glycol monobutyl ether, 3.6% by volume of ethylene glycol, 85.3% by volume of pure water) at 60 ° C. for 5 minutes. Then, the cured product is roughened by immersing the swollen cured product in a roughening aqueous solution (sodium permanganate 60 g / L, sodium hydroxide 45 g / L) at 80 ° C. for 5 minutes, The cured product obtained by roughening was cured by immersing it in a neutralizing solution (98% by mass sulfuric acid 5.0% by volume, hydroxylamine sulfate 0.8% by volume, pure water 94.2% by volume) at 40 ° C. for 5 minutes. Neutralize things.

  In the cured product, when the amount of film reduction satisfies the above range, the cured product of the prepreg or the fine wiring processability of the resin substrate can be improved. This is because the prepreg cured product or resin substrate having a film reduction amount defined by the above formula being equal to or less than the upper limit value can maintain the adhesion to the metal layer (circuit layer) even if the surface is roughened. It is considered to be a body.

  In order to achieve such a film reduction amount, maleimide compound (A), benzoxazine compound (B), inorganic filler (C), epoxy resin (D), low stress material (E), fiber substrate, It is important to appropriately control the type and blending amount of the curing accelerator, the prepreg production method, and the like.

  The thickness of the prepreg is, for example, 20 μm or more and 220 μm or less. When the thickness of the prepreg is within the above range, the balance between mechanical strength and productivity is particularly excellent, and a resin substrate suitable for a thin printed wiring board can be obtained.

  FIG. 1 is a cross-sectional view showing an example of the configuration of a metal-clad laminate 200 in the present embodiment. The metal-clad laminate 200 is provided with a metal foil 105 on one side or both sides of a cured product of prepreg (insulating layer 301) or a cured product of laminated body (insulating layer 301) in which two or more prepregs are stacked. The metal-clad laminate 200 can be used for forming an insulating layer of a printed wiring board.

It continues and the manufacturing method of a prepreg is demonstrated.
The prepreg is, for example, a sheet-like material obtained by impregnating the fiber base material with the resin composition (P) in the present embodiment and then semi-curing it. The sheet-like material having such a structure is excellent in various properties such as dielectric properties, mechanical and electrical connection reliability under high temperature and high humidity, and is suitable for manufacturing an insulating layer of a printed wiring board.

  The method for impregnating the fiber base material with the resin composition (P) is not particularly limited. For example, the resin composition (P) is dissolved in a solvent to prepare a resin varnish, and the fiber base material is immersed in the resin varnish. A method of applying the resin varnish to the fiber base material with various coaters, a method of spraying the resin varnish onto the fiber base material by spraying, a resin layer (P) comprising the resin composition (P) from both sides of the fiber base material And a method of laminating the fiber base material.

Next, a method for manufacturing the metal-clad laminate 200 using the prepreg obtained above will be described. A method for producing the metal-clad laminate 200 using prepreg is, for example, as follows.
Two or more prepregs or a laminate of two or more prepregs stacked on top and bottom or one side of the laminate are laminated with metal foil 105 and bonded together under high vacuum conditions using a laminator or becquerel device, or directly outside the prepreg. The metal foil 105 is stacked on both upper and lower surfaces or one surface. When two or more prepregs are stacked, the metal foil 105 is stacked on the outermost upper and lower surfaces or one surface of the stacked prepregs.
Subsequently, the metal-clad laminate 200 can be obtained by heat-pressing the laminate in which the prepreg and the metal foil 105 are stacked. Here, it is preferable to continue the pressurization until the end of cooling at the time of heat-pressure molding.

The heating temperature at the time of the above-described heating and pressing is preferably 120 ° C. or higher and 250 ° C. or lower, and more preferably 150 ° C. or higher and 240 ° C. or lower.
Moreover, the pressure at the time of the above-described heat and pressure molding is preferably 0.5 MPa or more and 5 MPa or less, and more preferably 2.5 MPa or more and 5 MPa or less.

  Further, after the heat and pressure molding, if necessary, post-curing may be performed in a thermostatic bath or the like. The post-curing temperature is preferably 150 ° C. or higher and 300 ° C. or lower, more preferably 250 ° C. or higher and 300 ° C. or lower.

  Moreover, a printed wiring board can be obtained using the metal-clad laminate 200 or the resin substrate as a core substrate.

  Hereinafter, each material used when manufacturing the prepreg, the metal-clad laminate 200, and the resin substrate will be described in detail.

Examples of the metal constituting the metal foil 105 include copper, a copper alloy, aluminum, an aluminum alloy, silver, a silver alloy, gold, a gold alloy, zinc, a zinc alloy, nickel, a nickel alloy, tin, Examples thereof include tin-based alloys, iron, iron-based alloys, Kovar (trade name), 42-alloy, invar, super-invar and other Fe—Ni-based alloys, W, Mo, and the like. Among these, the metal constituting the metal foil 105 is preferably copper or a copper alloy because of its excellent conductivity, easy circuit formation by etching, and low cost. That is, the metal foil 105 is preferably a copper foil.
Further, as the metal foil 105, a metal foil with a carrier or the like can also be used.
The thickness of the metal foil 105 is preferably 0.5 μm or more and 20 μm or less, and more preferably 1.5 μm or more and 18 μm or less.

Subsequently, the fiber base material used for this embodiment is demonstrated.
Although it does not specifically limit as a fiber base material, Glass fiber base materials, such as a glass woven fabric and a glass nonwoven fabric; Polyamide-type resin fibers, such as a polyamide resin fiber, an aromatic polyamide resin fiber, and a wholly aromatic polyamide resin fiber; Polyester resin fiber Polyester resin fibers such as aromatic polyester resin fibers and wholly aromatic polyester resin fibers; synthetic fiber base materials composed of woven or non-woven fabrics mainly composed of either polyimide resin fibers or fluororesin fibers; kraft paper , Cotton linter paper, or a paper base material mainly composed of linter and kraft pulp mixed paper. Any of these can be used. Among these, a glass fiber substrate is preferable. Thereby, a resin substrate with low water absorption, high strength, and low thermal expansion can be obtained.

Although the thickness of a fiber base material is not specifically limited, Preferably it is 5 micrometers or more and 150 micrometers or less, More preferably, they are 10 micrometers or more and 100 micrometers or less, More preferably, they are 12 micrometers or more and 90 micrometers or less. By using the fiber base material having such a thickness, the handling property at the time of producing the prepreg can be further improved.
When the thickness of the fiber base material is not more than the above upper limit, the impregnation property of the resin composition (P) in the fiber base material can be improved, and the occurrence of strand voids and a decrease in insulation reliability can be suppressed. Further, it is possible to facilitate formation of a through hole by a laser such as carbon dioxide, UV, or excimer. Moreover, the intensity | strength of a fiber base material or a prepreg can be improved as the thickness of a fiber base material is more than the said lower limit. As a result, handling properties can be improved, production of a prepreg can be facilitated, and warping of the resin substrate can be suppressed.

  As a glass fiber substrate, for example, glass fiber formed of one or more kinds of glass selected from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass and quartz glass A substrate is preferably used.

  Next, the printed wiring board 300 according to the present embodiment will be described. 2 and 3 are cross-sectional views showing an example of the configuration of the printed wiring board 300 in the present embodiment.

  The printed wiring board 300 includes at least an insulating layer 301 provided with a via hole 307 and a metal layer 303 provided on at least one surface of the insulating layer 301. In the present embodiment, the via hole 307 is a hole for electrically connecting the layers, and may be either a through hole or a non-through hole.

As shown in FIG. 2, the printed wiring board 300 according to the present embodiment may be a single-sided printed wiring board, a double-sided printed wiring board, or a multilayer printed wiring board. A double-sided printed wiring board is a printed wiring board in which a metal layer 303 is laminated on both sides of an insulating layer 301. The multilayer printed wiring board is a print in which two or more metal layers 303 are stacked on an insulating layer 301 via an interlayer insulating layer (also referred to as a buildup layer) by a plated through hole method, a buildup method, or the like. It is a wiring board.
Here, in the printed wiring board 300 according to the present embodiment, the insulating layer 301 corresponds to the insulating layer 301 of the resin substrate or the metal-clad laminate 200 according to the present embodiment.

  The metal layer 303 is a circuit layer, for example, and includes the metal foil 105 and / or the electroless metal plating film 308 and the electrolytic metal plating layer 309.

  When the printed wiring board 300 is a multilayer printed wiring board as shown in FIG. 3, the metal layer 303 is a circuit layer in the core layer 311 or the buildup layer 317.

  The metal layer 303 is formed by, for example, the SAP (semi-additive process) method on the surface of the metal foil 105 or the insulating layer 301 that has been subjected to chemical treatment or plasma treatment. After the electroless metal plating film 308 is applied on the metal foil 105 or the insulating layer 301, the non-circuit forming portion is protected by a plating resist, the electrolytic metal plating layer 309 is applied by electrolytic plating, the plating resist is removed, and flash etching is performed. The metal layer 303 is formed on the metal foil 105 or the insulating layer 301 by removing the electroless metal plating film 308 by the above.

  The circuit dimension of the metal layer 303 can be 25 μm / 25 μm or less, particularly 15 μm / 15 μm or less, when expressed in line and space (L / S). If the circuit dimensions are reduced and the wiring is made fine, the insulation reliability between the wirings decreases. However, the printed wiring board 300 according to the present embodiment is capable of fine wiring with a line and space (L / S) of 15 μm / 15 μm or less, and the line and space (L / S) can be refined to about 10 μm / 10 μm. Can be achieved.

  The thickness of the metal layer 303 is not particularly limited, but is usually 5 μm or more and 25 μm or less.

The insulating layer 305 in the buildup layer 317 is not particularly limited as long as it is made of an insulating material, but can be made of, for example, a resin film or a prepreg. Among these, the prepreg is a sheet-like material, and has excellent dielectric properties, various characteristics such as mechanical and electrical connection reliability under high temperature and high humidity, and is suitable for manufacturing a build-up layer 317 for a printed wiring board. preferable.
As the prepreg, the prepreg described above is particularly preferable.

  The thickness of the insulating layer 301 in the core layer 311 (including the insulating layer 301 in the printed wiring board 300 not including the build-up layer 317) is preferably 0.025 mm or more and 0.3 mm or less. When the thickness of the insulating layer 301 is within the above range, the balance between mechanical strength and productivity is particularly excellent, and the insulating layer 301 suitable for a thin printed wiring board can be obtained.

  The thickness of the insulating layer 305 in the buildup layer 317 is preferably 0.015 mm or more and 0.05 mm or less. When the thickness of the insulating layer 305 is within the above range, the balance between mechanical strength and productivity is particularly excellent, and the insulating layer 305 suitable for a thin printed wiring board can be obtained.

  Next, an example of a method for manufacturing the printed wiring board 300 will be described. However, the method for manufacturing the printed wiring board 300 according to the present embodiment is not limited to the following example.

First, the metal-clad laminate 200 is prepared.
Next, part or all of the metal foil 105 is removed by etching.

Next, a via hole 307 is formed in the insulating layer 301. The via hole 307 can be formed using, for example, a drilling machine or laser irradiation. Examples of the laser used for laser irradiation include an excimer laser, a UV laser, and a carbon dioxide gas laser. Resin residues and the like after forming the via hole 307 may be removed by an oxidizing agent such as permanganate or dichromate.
Note that the via hole 307 may be formed in the insulating layer 301 before the metal foil 105 is removed by the etching treatment.

Next, a chemical treatment or a plasma treatment is performed on the surface of the metal foil 105 or the insulating layer 301.
The chemical treatment is not particularly limited, and examples thereof include a method using an oxidizing agent solution having an organic substance decomposing action. Examples of the plasma treatment include a method of directly irradiating a target object with active species (plasma, radical, etc.) having a strong oxidizing action to remove organic residue.

  Next, the metal layer 303 is formed. The metal layer 303 can be formed by, for example, a semi-additive process (SAP) or a modified semi-additive process (MSAP). This will be specifically described below.

  First, an electroless metal plating film 308 is formed on the surface of the metal foil 105 or the insulating layer 301 or in the via hole 307 by using an electroless plating method, and conduction between both surfaces of the printed wiring board 300 is achieved. The via hole 307 can be appropriately filled with a conductor paste or a resin paste. An example of the electroless plating method will be described. For example, first, catalyst nuclei are provided on the surface of the metal foil 105 or the insulating layer 301 or in the via hole 307. The catalyst nucleus is not particularly limited. For example, a noble metal ion or palladium colloid can be used. Subsequently, an electroless metal plating film 308 is formed by electroless plating using the catalyst nucleus as a nucleus. For the electroless plating treatment, for example, a material containing copper sulfate, formalin, complexing agent, sodium hydroxide or the like can be used. In addition, it is preferable to heat-process 100-250 degreeC after electroless plating, and to stabilize a plating film. A heat treatment at 120 to 180 ° C. is particularly preferable in that a film capable of suppressing oxidation can be formed. Moreover, the average thickness of the electroless metal plating film 308 is, for example, about 0.1 to 2 μm.

  Next, a plating resist having a predetermined opening pattern is formed on the metal foil 105 and / or the electroless metal plating film 308. This opening pattern corresponds to, for example, a circuit pattern. The plating resist is not particularly limited, and known materials can be used, but liquid and dry films can be used. In the case of forming fine wiring, it is preferable to use a photosensitive dry film or the like as the plating resist. An example using a photosensitive dry film will be described. For example, a photosensitive dry film is laminated on the electroless metal plating film 308, the non-circuit formation region is exposed and photocured, and the unexposed portion is dissolved and removed with a developer. A plating resist is formed by leaving the cured photosensitive dry film.

  Next, an electrolytic metal plating layer 309 is formed by electroplating at least inside the opening pattern of the plating resist and on the metal foil 105 and / or the electroless metal plating film 308. Although it does not specifically limit as an electroplating process, The well-known method used with a normal printed wiring board can be used, For example, in the state immersed in plating solutions, such as copper sulfate, an electric current is supplied to a plating solution. A method such as flowing can be used. The electrolytic metal plating layer 309 may be a single layer or may have a multilayer structure. The material of the electrolytic metal plating layer 309 is not particularly limited, and for example, any one or more of copper, copper alloy, 42 alloy, nickel, iron, chromium, tungsten, gold, and solder can be used.

  Next, the plating resist is removed using an alkaline stripping solution, sulfuric acid, a commercially available resist stripping solution, or the like.

  Next, the metal foil 105 and / or the electroless metal plating film 308 other than the region where the electrolytic metal plating layer 309 is formed are removed. For example, the metal foil 105 and / or the electroless metal plating film 308 can be removed by using soft etching (flash etching) or the like. Here, the soft etching treatment can be performed, for example, by etching using an etchant containing sulfuric acid and hydrogen peroxide. Thereby, the metal layer 303 can be formed. The metal layer 303 is constituted by the metal foil 105 and / or the electroless metal plating film 308 and the electrolytic metal plating layer 309.

  Furthermore, a build-up layer 317 can be stacked on the printed wiring board 300 as necessary, and the steps of interlayer connection and circuit formation by a semi-additive process can be repeated to form a multilayer.

  The printed wiring board 300 of this embodiment is obtained by the above.

  Next, the semiconductor device 400 according to the present embodiment will be described. 4 and 5 are cross-sectional views showing an example of the configuration of the semiconductor device 400 according to the present embodiment. The printed wiring board 300 can be used in a semiconductor device 400 as shown in FIGS. A method for manufacturing the semiconductor device 400 is not particularly limited, and examples thereof include the following method.

  First, a build-up layer is laminated on the metal layer 303 (circuit layer) as necessary, and the steps of interlayer connection and circuit formation by a semi-additive process are repeated. And the soldering resist layer 401 is laminated | stacked on the both surfaces or single side | surface of the printed wiring board 300 as needed.

  The method of forming the solder resist layer 401 is not particularly limited. For example, a method of forming by laminating, exposing and developing a dry film type solder resist, or exposing and developing a liquid resist printed This is done by the forming method.

  Subsequently, by performing a reflow process, the semiconductor element 407 is fixed to the connection terminal which is a part of the circuit layer via the solder bump 410. Thereafter, the semiconductor device 400 as shown in FIGS. 4 and 5 is obtained by sealing the semiconductor element 407, the solder bump 410, and the like with the sealing material 413.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable. For example, in this embodiment, although the case where the prepreg is one layer was shown, you may produce an insulating layer using what laminated | stacked two or more layers of prepregs.
Moreover, in the said embodiment, although the semiconductor element 407 and the circuit layer of the printed wiring board 300 were connected by the solder bump 410, it is not restricted to this. For example, the semiconductor element 407 and the circuit layer of the printed wiring board 300 may be connected by a bonding wire.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these. In addition, in an Example, unless otherwise specified, a part represents a mass part. Moreover, each thickness is represented by the average film thickness.

In the examples and comparative examples, the following raw materials were used.
Maleimide compound 1: Bismaleimide compound represented by the formula (a1) (BMI-1500, manufactured by Designa Molecules, Inc., molecular weight 1500)
Maleimide compound 2: Bismaleimide compound represented by the formula (a2) (BMI-1700, manufactured by Designa Molecules Co., Ltd., molecular weight 1700)
Maleimide compound 3: Bismaleimide compound represented by the formula (a3) (BMI-3000, manufactured by Designa Molecules Co., Ltd., molecular weight 3000)
Maleimide compound 4: a compound represented by formula (1), wherein n ₁ is 0 or more and 3 or less, X ₁ is a group represented by “—CH ₂ —”, a is 0, and b is 0 (BMI-2300, Yamato Kasei) Industrial company, Mw = 750)
Maleimide compound 5: 1,6′-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH, manufactured by Daiwa Kasei Kogyo Co., Ltd.)
Maleimide compound 6: 4,4′-diphenylmethane bismaleimide (in the formula (1), n ₁ is 0, X ₁ is a group represented by “—CH ₂ —”, a is 0, b is 0, (BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd.)

Benzoxazine compound 1: benzoxazine compound represented by formula (2-1) (Pd-type benzoxazine, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Benzoxazine compound 2: benzoxazine compound represented by formula (3-1) (Fa type benzoxazine manufactured by Shikoku Kasei Kogyo Co., Ltd.)

Epoxy resin 1: Aralkyl epoxy resin (NC3000L, Nippon Kayaku Co., Ltd.)
Epoxy resin 2: bisphenol F type epoxy resin (EPICLON 830S, manufactured by DIC Corporation)
Epoxy resin 3: Naphthalene diol type epoxy resin (EPICLON HP-4032D, manufactured by DIC Corporation)

  Inorganic filler 1: Silica (manufactured by Admatech, SC4050, average particle size 1.1 μm, silica slurry treated with phenylaminosilane)

Low-stress material 1: carboxylic acid-terminated acrylonitrile / butazine rubber (manufactured by PTI Japan, CTBN1008SP)
Low stress material 2: Amino group-terminated acrylonitrile / butazine rubber (manufactured by PTI Japan, ATBN1300X16)
Low stress material 3: Silicone compound (epoxy group and phenyl group-containing three-dimensional cross-linked silicone resin, manufactured by Toray Dow Corning, AY42-119)
Low stress material 4: Silicone compound (silicone epoxy resin, manufactured by Momentive Performance Materials, TSL9906)
Low stress material 5: silicone compound (modified silicone resin having amino groups at both ends of molecular chain, manufactured by Toray Dow Corning, BY16-853)
Low stress material 6: acrylic block copolymer (block copolymer of acrylic monomer (PMMA-b-PBA-b-PMMA; b = block), number average molecular weight: about 10,000, manufactured by Arkema, Nano Strength M51)
Low stress material 7: acrylic copolymer (acrylic copolymer, average molecular weight: about 150,000, manufactured by Nagase ChemteX Corporation, SG-P3Mw4)

Curing accelerator 1: 2-phenylimidazole (manufactured by Shikoku Kasei Co., Ltd., 2PZ-PW)
Curing accelerator 2: Tetraphenylphosphonium tetra-p-tolylborate (manufactured by Hokuko Chemical Co., Ltd., TPP-MK)

  Next, production of the prepreg will be described. The composition of the resin varnish used is shown in Table 1 (parts by mass), and the thicknesses and the like of the obtained prepregs 1 to 19 are shown in Table 2. In addition, P1-P19 of Table 2 means prepreg 1-prepreg 19.

[1] Prepreg 1
1. Preparation of Resin Varnish 1 Each component was dissolved or dispersed at a solid content ratio shown in Table 1, and adjusted so as to have a nonvolatile content of 70% by mass with methyl ethyl ketone, and stirred using a high-speed stirrer to prepare Resin Varnish 1.

2. Manufacture of prepreg (prepreg 1)
A glass woven fabric (cross type # 2118, T glass, basis weight 114 g / m ² ) is impregnated with a resin varnish 1 with a coating apparatus, dried with a hot air drying apparatus at 140 ° C. for 10 minutes, and a prepreg 1 having a thickness of 106 μm ( P1) was obtained.

(Prepreg 2-19)
Prepregs 2 to 19 were produced in the same manner as prepreg 1 except that the types of resin varnishes were changed as shown in Tables 1 and 2. However, varnish 19 adjusted the solid content concentration with dimethylformamide from the viewpoint of solubility.

Example 1
1. Production of Resin Substrate Super thin copper foil (Mitsui Metal Mining Co., Ltd., Micro Thin Ex, 2.0 μm) is superimposed on both sides of the prepreg 1, and the resin is formed by heating and pressing at a pressure of 4 MPa and a temperature of 230 ° C. for 2 hours. A substrate was obtained. The thickness of the core layer (part consisting of the resin substrate) of the obtained resin substrate with metal foil was 0.107 mm.

2. Fabrication of printed wiring board After the rough thin copper foil layer on the surface of the resin board with metal foil obtained in the previous section is roughened to about 1μm, a through hole of φ80μm for interlayer connection is formed with a carbon dioxide laser did. Next, it is immersed in a 60 ° C. swelling liquid (Atotech Japan, Swelling Dip Securigant P) for 5 minutes, and further immersed in an 80 ° C. aqueous potassium permanganate solution (Atotech Japan, Concentrate Compact CP) for 2 minutes. Then, it neutralized and the desmear process in a through hole was performed. Next, electroless copper plating was performed at a thickness of 0.5 μm, a resist layer for electrolytic copper plating was formed at a thickness of 18 μm, pattern copper plating was performed, and post-curing was performed by heating at a temperature of 150 ° C. for 30 minutes. Next, the plating resist was removed and the entire surface was flash etched to form a pattern of L / S = 15/15 μm.

(Examples 2 to 18 and Comparative Example 1)
A resin substrate and a printed wiring board were produced in the same manner as in Example 1 except that the type of prepreg was changed to that shown in Table 2.

  In addition, the following evaluations were performed on the resin substrates obtained in the examples and comparative examples. The evaluation results are shown in Table 2.

(1) Glass transition temperature The glass transition temperature was measured by dynamic viscoelasticity measurement (DMA device, manufactured by TA Instruments, Q800).
A test piece of 8 mm × 40 mm was cut out from the obtained resin substrate, and the copper foil was removed with an etching solution (ferric chloride solution, 35 ° C.) to obtain a cured product of prepreg. Next, dynamic viscoelasticity measurement was performed at a heating rate of 5 ° C./min and a frequency of 1 Hz using the obtained prepreg cured product. The glass transition temperature was a temperature at which tan δ had a maximum value at a frequency of 1 Hz.

(2) Storage elastic modulus E '
The storage elastic modulus E ′ was measured by dynamic viscoelasticity measurement (DMA device, manufactured by TA Instruments, Q800). A test piece of 8 mm × 40 mm was cut out from the obtained resin substrate, and the copper foil was removed with an etching solution (ferric chloride solution, 35 ° C.) to obtain a cured product of prepreg.
Using the obtained cured prepreg, the storage elastic modulus was measured at 30 ° C. and 250 ° C. at a heating rate of 5 ° C./min and at a frequency of 1 Hz, and the storage elastic modulus E ′ _{30 at 30} ° C. was 250 ° C. The storage elastic moduli E ′ ₂₅₀ and E ′ ₃₀ / E ′ ₂₅₀ were calculated.

(3) Dimensional Shrinkage A test piece of 4 mm × 15 mm was cut out from the obtained resin substrate, and the copper foil was removed with an etching solution (ferric chloride solution, 35 ° C.) to obtain a cured product of prepreg. Next, for the cured product of the obtained prepreg, from a temperature of 30 ° C. using a thermomechanical analyzer TMA (TA Instruments, Q400) at a heating rate of 10 ° C./min, a load of 10 g, and a compression mode. Thermomechanical analysis measurement was performed, which consisted of a process of raising the temperature to 260 ° C. and a process of maintaining at 260 ° C. for 1 hour. Then, the maximum thermal expansion amount L ₁ from the reference length L ₀ of the cured prepreg and the thermal expansion amount L ₂ from the reference length L ₀ when the cured prepreg was held at 260 ° C. for 1 hour were determined. Next, a dimensional shrinkage ratio represented by 100 × (L ₁ −L ₂ ) / L ₀ was calculated.

(4) Linear expansion coefficient A test piece of 4 mm x 15 mm was cut out from the obtained resin substrate, and the copper foil was removed with an etching solution (ferric chloride solution, 35 ° C) to obtain a cured product of prepreg. Subsequently, with respect to the cured product of the obtained prepreg, using a thermomechanical analyzer TMA (TA Instruments, Q400), a temperature range of 30 to 260 ° C., a heating rate of 10 ° C./min, a load of 10 g, and compression Thermomechanical analysis (TMA) was measured for 2 cycles under mode conditions. The average value α ₁ of the linear expansion coefficient in the plane direction (XY direction) in the range of 50 ° C. to 150 ° C. and the average value α ₂ of the linear expansion coefficient in the plane direction (XY direction) in the range of 150 ° C. to 250 ° C. were calculated. .
In addition, the value of the 2nd cycle was employ | adopted for the expansion coefficient.

(5) Film reduction amount A test piece of 4 mm × 15 mm was cut out from the obtained resin substrate, and the copper foil was removed with an etching solution (ferric chloride solution, 35 ° C.) to obtain a cured product of prepreg. Next, the mass after drying at 120 ° C. for 1 hour of the cured product of the obtained prepreg is defined as a first mass, and the mass after drying for 1 hour at 120 ° C. of the cured product after treating the cured product under the following conditions. When it was set as the second mass, the amount of film reduction defined by [{(first mass) − (second mass)} / (sum of areas of both sides of the cured product)] × 100 was calculated. .
<Conditions>
The cured product is immersed in a 3 g / L sodium hydroxide solution (solvent: 11.1% by volume of diethylene glycol monobutyl ether, 3.6% by volume of ethylene glycol, 85.3% by volume of pure water) at 60 ° C. for 5 minutes. Then, the cured product is roughened by immersing the swollen cured product in a roughening aqueous solution (sodium permanganate 60 g / L, sodium hydroxide 45 g / L) at 80 ° C. for 5 minutes, The cured product obtained by roughening was cured by immersing it in a neutralizing solution (98% by mass sulfuric acid 5.0% by volume, hydroxylamine sulfate 0.8% by volume, pure water 94.2% by volume) at 40 ° C. for 5 minutes. Neutralize things

(6) Evaluation of insulation reliability between thin wires A test sample was prepared by laminating and curing a build-up material (BLA-3700GS, manufactured by Sumitomo Bakelite Co., Ltd.) on a fine circuit pattern of L / S = 15/15 μm of a printed wiring board. . Using this test sample, the continuous humidity insulation resistance was evaluated under the conditions of a temperature of 130 ° C., a humidity of 85%, and an applied voltage of 3.3 V. A resistance value of 10 ⁶ Ω or less was regarded as a failure. The evaluation criteria are as follows.
◎: No failure for 500 hours or more ○: There is a failure in 200 to less than 500 hours (substantially no problem)
×: Failure occurred in less than 200 hours

(7) Evaluation of fine wire workability In the production of the above-described printed wiring board, the printed wiring board after forming a fine circuit pattern of L / S = 15/15 μm was evaluated by a thin wire appearance inspection and a continuity check with a laser microscope. . The evaluation criteria are as follows.
◎: No problem in both shape and continuity 〇: No short circuit or wire breakage, no problem ×: Short circuit, wire breakage

(8) Evaluation of through-hole insulation reliability In manufacturing the printed wiring board described above, 20 pairs of through-holes of Φ80 μm for interlayer connection were formed with 80 μm between walls. Next, a test sample in which a build-up material (manufactured by Sumitomo Bakelite, BLA-3700GS) was laminated and cured on the circuit pattern was produced. Using this test sample, the insulation resistance in continuous humidity was evaluated under the conditions of a temperature of 130 ° C., a humidity of 85%, and an applied voltage of 5.5V. A resistance value of 10 ⁶ Ω or less was regarded as a failure. The evaluation criteria are as follows.
A: No failure for 500 hours or more (good)
○: There is a failure in less than 200 to 500 hours (substantially no problem)
Δ: Failure in less than 200 hours (substantially unusable)
×: Failure occurred in less than 100 hours (cannot be used)

(9) Warpage evaluation of semiconductor device Build-up material (BLA-3700GS, manufactured by Sumitomo Bakelite Co., Ltd.) was laminated and cured on the printed wiring board after the circuit pattern was formed, and circuit processing was performed by a semi-additive method. A 10 mm × 10 mm × 100 μm thick semiconductor element with solder bumps was mounted thereon, sealed with an underfill (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4160G), and cured at 150 ° C. for 2 hours. Finally, a semiconductor device was manufactured by dicing to 15 mm × 15 mm.
The warpage of the obtained semiconductor device at 260 ° C. was evaluated using a temperature variable laser three-dimensional measuring machine (manufactured by Hitachi Technology and Service, model LS220-MT100MT50). The semiconductor element surface was placed in the sample chamber of the measuring machine, the displacement in the height direction was measured, and the largest value of the displacement difference was taken as the amount of warpage. The evaluation criteria are as follows.
A: Warpage amount is less than 30 μm 〇: Warpage amount is 30 μm or more and less than 50 μm ×: Warpage amount is 50 μm or more

(10) Heat cycle test Four semiconductor devices obtained in (9) were treated at 85 ° C. and 85% for 168 hours, then treated three times in an IR reflow furnace (peak temperature: 260 ° C.), and in the atmosphere And 500 cycles at −55 ° C. (15 minutes) and 125 ° C. (15 minutes). Next, using an ultrasonic imaging apparatus (manufactured by Hitachi Construction Machinery Finetech Co., Ltd., FS300), the semiconductor element and the solder bump were observed for abnormalities.
A: No abnormality in both semiconductor element and solder bump O: Cracks are found in some of the semiconductor elements and / or solder bumps, but there are no practical problems ×: Cracks appear in some or all of the semiconductor elements and / or solder bumps There are practical problems

105 Metal foil 200 Metal-clad laminate 300 Printed wiring board 301 Insulating layer 303 Metal layer 305 Insulating layer 307 Via hole 308 Electroless metal plating film 309 Electrolytic metal plating layer 311 Core layer 317 Buildup layer 400 Semiconductor device 401 Solder resist layer 407 Semiconductor Element 410 Solder bump 413 Sealing material

Claims (26)

A thermosetting resin composition used for forming an insulating layer in a printed wiring board,
Including a maleimide compound (A),
The resin composition for printed wiring boards in which the maleimide compound (A) contains at least a bismaleimide compound (A1) represented by the following formula (a).

(In the formula (a), Q is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 6 or more carbon atoms, P is a divalent atom or organic group, and n Is an integer from 1 to 10. In the resin composition for printed wiring boards according to claim 1,
A resin composition for a printed wiring board, wherein the maleimide compound (A) further comprises a different type of maleimide compound (A2) from the bismaleimide compound (A1). In the resin composition for printed wiring boards according to claim 2,
The resin composition for a printed wiring board, wherein the maleimide compound (A2) contains at least one selected from a maleimide compound represented by the following formula (1) and 1,6′-bismaleimide- (2,2,4-trimethyl) hexane object.

(In Formula (1), n ₁ is an integer of 0 to 10, X ₁ is each independently an alkylene group having 1 to 10 carbon atoms, a group represented by Formula (1a) below, a formula “— A group represented by “SO ₂ —”, a group represented by “—CO—”, an oxygen atom or a single bond, each R ₁ is independently a hydrocarbon group having 1 to 6 carbon atoms, and a is Each independently represents an integer of 0 or more and 4 or less, and b is independently an integer of 0 or more and 3 or less)

(In the formula (1a), Y is a hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring, and n ₂ is an integer of 0 or more.) In the resin composition for printed wiring boards as described in any one of Claims 1 thru | or 3,
A resin composition for printed wiring boards, further comprising a benzoxazine compound (B). In the resin composition for printed wiring boards according to claim 4,
The said benzoxazine compound (B) is a resin composition for printed wiring boards containing 1 type, or 2 or more types selected from the compound shown by following formula (2), and the compound shown by following formula (3).

(In the formula (2), each X ₂ independently represents an alkylene group having 1 to 10 carbon atoms, a group represented by the formula (1a), a group represented by the formula “—SO ₂ —”, “— A group represented by “CO—”, an oxygen atom or a single bond, R ₂ is each independently a hydrocarbon group having 1 to 6 carbon atoms, and c is each independently an integer of 0 or more and 4 or less)

(In the formula (3), X ₃ each independently represents an alkylene group having 1 to 10 carbon atoms, a group represented by the formula (1a), a group represented by the formula “—SO ₂ —”, “— A group represented by "CO-", an oxygen atom or a single bond, each R ₃ is independently a hydrocarbon group having 1 to 6 carbon atoms, and d is each independently an integer of 0 or more and 4 or less) In the resin composition for printed wiring boards according to claim 5,
The benzoxazine compound (B) is a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), a compound represented by the following formula (2-3), the following formula (3-1) ), A compound represented by the following formula (3-2) and a compound represented by the following formula (3-3).

(In the formula (2-3), each R is independently a hydrocarbon group having 1 to 4 carbon atoms) In the resin composition for printed wiring boards as described in any one of Claims 4 thru | or 6,
The resin composition for a printed wiring board, wherein the content of the maleimide compound (A) is 35% by mass to 80% by mass with respect to 100% by mass in total of the maleimide compound (A) and the benzoxazine compound (B). . In the resin composition for printed wiring boards as described in any one of Claims 1 thru | or 7,
A printed wiring board resin composition further comprising a low stress material (E). In the resin composition for printed wiring boards according to claim 8,
The low stress material (E) is a (meth) acrylic block copolymer; a silicone compound; an acrylonitrile-butadiene rubber modified with a carboxyl group, an amino group, a vinyl acrylate group or an epoxy group; an aliphatic epoxy resin; and rubber particles The resin composition for printed wiring boards containing 1 type, or 2 or more types selected from. In the resin composition for printed wiring boards as described in any one of Claims 1 thru | or 9,
A printed wiring board resin composition further comprising an inorganic filler (C). In the resin composition for printed wiring boards according to claim 10,
A resin composition for a printed wiring board, wherein the inorganic filler (C) contains one or more selected from talc, alumina, glass, silica, mica, boehmite, aluminum hydroxide, and magnesium hydroxide. In the resin composition for printed wiring boards according to claim 10 or 11,
The resin composition for printed wiring boards whose content of the said inorganic filler (C) is 50 to 85 mass% with respect to 100 mass% of total solid content of the said resin composition for printed wiring boards. In the resin composition for printed wiring boards as described in any one of Claims 1 thru | or 12,
A printed wiring board resin composition further comprising an epoxy resin (D). In the resin composition for printed wiring boards according to claim 13,
The content of the epoxy resin (D) is 1% by mass or more and 50% by mass or less when the total amount of the components excluding the inorganic filler (C) in the resin composition for printed wiring board is 100% by mass. A printed wiring board resin composition.   A prepreg formed by impregnating a fiber base material with the resin composition for a printed wiring board according to any one of claims 1 to 14. The prepreg according to claim 15, wherein
The glass transition temperature of a cured product obtained by heat-treating the prepreg at 230 ° C. for 2 hours, which is measured by dynamic viscoelasticity measurement under conditions of a heating rate of 5 ° C./min and a frequency of 1 Hz, is 250 ° C. or higher. Prepreg. The prepreg according to claim 15 or 16,
The ratio (E ′ ₃₀ / E ′ ₂₅₀ ) of the storage elastic modulus E ′ ₃₀ at 30 ° C. to the storage elastic modulus E ′ ₂₅₀ at 250 ° C. of the cured product obtained by heat-treating the prepreg at 230 ° C. for 2 hours. A prepreg of 1.05 or more and 1.75 or less. The prepreg according to any one of claims 15 to 17,
Average calculated in the range of 150 ° C. to 250 ° C. with respect to the average linear expansion coefficient α ₁ calculated in the range of 50 ° C. to 150 ° C. in the in-plane direction of the cured product obtained by heat treatment of the prepreg at 230 ° C. for 2 hours. A prepreg having a linear expansion coefficient α ₂ ratio (α ₂ / α ₁ ) of 0.7 or more and 2.0 or less. The prepreg according to any one of claims 15 to 18,
For the cured product obtained by heat-treating the prepreg at 230 ° C. for 2 hours,
Using a thermomechanical analyzer
When the thermomechanical analysis measurement comprising the process of raising the temperature from 30 ° C to 260 ° C at 10 ° C / min and the process of maintaining at 260 ° C for 1 hour is performed, the longitudinal direction of the cured product before the thermomechanical analysis measurement and the length of the the reference length L _0, the maximum amount of thermal expansion from the reference length L ₀ of the cured product and L _1, from the reference length L ₀ when the cured product was held for 1 hour at 260 ° C. When the amount of thermal expansion of L ₂ is
A prepreg having a dimensional shrinkage represented by 100 × (L ₁ −L ₂ ) / L ₀ of 0.15% or less. The prepreg according to any one of claims 15 to 19,
When the mass of the cured product obtained by heat-treating the prepreg at 230 ° C. for 2 hours is the first mass, and the mass of the cured product after treating the cured product under the following conditions is the second mass,
[{(1st mass)-(2nd mass)} / (sum of the areas of the front and back surfaces of the cured product)] × 100 The prepreg whose film reduction amount defined by 100 is 1.2 g / m ² or less .
<Conditions>
By immersing the cured product in a 3 g / L sodium hydroxide solution (solvent: diethylene glycol monobutyl ether 11.1% by volume, ethylene glycol 3.6% by volume, pure water 85.3% by volume) at 60 ° C. for 5 minutes. The cured product is swollen, and then the cured product is roughened by immersing the swollen cured product in a roughening solution (sodium permanganate 60 g / L, sodium hydroxide 45 g / L) at 80 ° C. for 5 minutes. The cured product that has been treated and then roughened is then added to a neutralization solution (98% by mass sulfuric acid 5.0% by volume, hydroxylamine sulfate 0.8% by volume, pure water 94.2% by volume) at 40 ° C. for 5 minutes. Neutralize the cured product by dipping The prepreg according to any one of claims 15 to 20,
The fiber substrate is a glass fiber substrate formed of one or more kinds of glass selected from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass and quartz glass. A prepreg. The prepreg according to any one of claims 15 to 21,
A prepreg having a thickness of 20 μm or more and 220 μm or less.   A resin substrate comprising a cured product of the prepreg according to any one of claims 15 to 22.   A metal-clad laminate in which a metal foil is provided on one or both sides of a cured product of the prepreg according to any one of claims 15 to 22 or a cured product of a laminate obtained by superimposing two or more prepregs.   A printed wiring board obtained by processing a circuit of the resin substrate according to claim 23 or the metal-clad laminate according to claim 24, wherein one or two or more circuit layers are provided.   The semiconductor device which mounted the semiconductor element on the said circuit layer of the printed wiring board of Claim 25.

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