JP6550872B2 - Resin composition for printed wiring board, prepreg, resin substrate, metal-clad laminate, printed wiring board, and semiconductor device - Google Patents

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, with the demand for higher functionality of electronic devices, high density integration and further high density mounting of electronic components are in progress, and miniaturization of semiconductor devices used in these electronic devices is rapidly advancing. 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, the surface of the insulating layer is roughened to form an electroless metal plating film as a base 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 formation portion is removed by flash etching to form 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 regarding such a printed wiring board, the thing of the following patent documents 1 is mentioned, for example. 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. A printed wiring board using a thermosetting composition characterized in that it is 3 to 30% by weight based on the total amount of the thermosetting resin and the thermosetting resin having 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 demand is particularly remarkable with the recent increase in the density of wiring 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）

（前記式（ａ３）において、ｎは１以上１０以下の整数である）

（前記式（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、前記式（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１〜６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）

（前記式（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、前記式（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１〜６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） According to the invention
A thermosetting resin composition used for forming an insulating layer in a printed wiring board,
A maleimide compound (A) and a benzoxazine compound (B) ,
The maleimide compound (A) contains at least one bismaleimide compound (A1) selected from a compound represented by the following formula (a) and a compound represented by the formula (a3) ,
A resin composition for a printed wiring board is provided, wherein the benzoxazine compound (B) contains at least one selected from a compound represented by the following formula (2) and a compound represented by the following formula (3) .

(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 an organic group, n Is an integer from 1 to 10.

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

(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)

  Furthermore, according to the present invention, there is provided a prepreg obtained by impregnating the above-mentioned resin composition for a printed wiring board in a fiber base material.

  Furthermore, according to the present invention, there is provided a resin substrate containing a cured product of the above prepreg.

  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 obtained by circuit processing the above-mentioned resin substrate or the above-mentioned metal-clad laminate and 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 having fine circuit dimensions and capable of realizing a printed wiring board excellent in insulation reliability under high temperature and high humidity, a prepreg, a resin substrate, and high temperature and high humidity It is possible to provide a printed wiring board and a semiconductor device which are excellent in insulation reliability in

It is a sectional view showing an example of composition of a metal tension laminate sheet 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 a sectional view showing an example of composition of a semiconductor device in this embodiment. It is a sectional view showing an example of composition of a semiconductor device in this embodiment.

  Hereinafter, embodiments of the present invention will be described using the drawings. In all the drawings, similar constituent elements are denoted by common reference numerals, and description thereof is omitted as appropriate. Also, the figure is a schematic view 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. , A maleimide compound (A). And the said maleimide compound (A) contains at least the bismaleimide compound (A1) shown by a 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 an organic group, 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. Based on the above-mentioned findings, the present inventors further studied intensively. 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 a small thermal shrinkage at high temperatures, so that the adhesion between the insulating layer and the circuit layer can be maintained even if the temperature change is severed 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, since the insulating layer formed of the resin composition (P) has a small thermal shrinkage at high temperatures, the stress generated between the semiconductor element and the printed wiring board is reduced even if the temperature change is severed for a long time 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) contains 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 an organic group, 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 which contains at least one or more of these atoms or organic groups is mentioned. Examples of the organic group containing 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 structures other than those described above. As P in that case, a group represented by the following chemical formula can be exemplified.

  As a specific example of such a bismaleimide compound (A1), 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 etc. which are shown are mentioned. As a specific example of the bismaleimide compound shown by Formula (a1), BMI-1500 (The dignaner moleculars company make, molecular weight 1500) etc. are mentioned. 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%. % Or more and 100% by mass or less is preferable, 1% by mass or more and 95% by mass or less is more preferable, 10% by mass or more and 75% by mass or less is more preferable, and 30% by mass or more and 75% by mass or less is particularly preferable. When the content of the bismaleimide compound (A1) is within the above range, the balance between low heat shrinkage and chemical resistance of the cured product of the obtained prepreg 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. Although the upper limit in particular of Mw is not limited, Mw 4000 or less is preferred, and Mw 2500 or less is more preferred. 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).
As such a maleimide compound (A2), for example, a maleimide compound represented by the following formula (1); 1,6′-bismaleimide- (2,2,4-trimethyl) hexane, hexamethylenediamine bismaleimide, N Aliphatic bismaleimide compounds such as N, N'-1,2-ethylenebismaleimide, N, N'-1,3-propylenebismaleimide, N, N'-1,4-tetramethylene bismaleimide, etc. 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 the formula (1), n ₁ is an integer of 0 to 10, and X ₁ is each 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 Independently, it is an integer of 0 or more and 4 or less, and b is each 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. Groups, pentamethylene groups, hexamethylene groups and the like.

Moreover, as a branched alkylene group, specifically, —C (CH ₃ ) ₂ — (isopropylene group), —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C An alkylmethylene group such as (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2- ; -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.

In addition, R ₁ is each independently a hydrocarbon group having 1 to 6 carbon atoms, but 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 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 having an aromatic ring may be composed of only an aromatic ring, or may have a hydrocarbon group other than an aromatic ring. The aromatic ring which Y has may be one or two or more, and in the case of two or more, these aromatic rings may be same or different. The aromatic ring may be any of a single ring structure and a multiple ring 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. The bivalent group which removed two hydrogen atoms from the nucleus of the compound which has family nature is mentioned.

  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. As a substituent, an alkyl group is mentioned, for example.

  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 a group represented by either of. 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, it is particularly preferably 1 or 2.

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 a maleimide compound (A2) shown by the said Formula (1), the maleimide compound shown by following formula (1-1) is used especially preferable, for example.

  The resin composition (P) preferably further contains a benzooxazine compound (B) from the viewpoint of further improving the low thermal shrinkage and chemical resistance of the cured product of the obtained prepreg and the resin substrate. The benzoxazine compound (B) is a compound having a benzoxazine ring. As a benzoxazine compound (B), 1 type, or 2 or more types selected from the compound shown by following formula (2) and the compound shown by following formula (3) are mentioned.

（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 above formula (3), X ₃ each 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, 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 ones as described for X ₁ in the above formula (1). Further, 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), and further, 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).

  Among such compounds represented by the above formula (2) and compounds represented by the above formula (3), such benzoxazine compounds (B) are compounds represented by the above formula (2) preferable. Thereby, the insulating layer obtained from the resin composition (P) exhibits more excellent low heat shrinkage and chemical resistance.

In the compound represented by the above 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 Preferably, c is 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.

  As preferable specific examples of the benzoxazine compound (B), for example, 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) And one or more selected from a compound represented by the following formula (3-1), a compound represented by the following formula (3-2), and a compound 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 of the resin composition (P) (that is, the components excluding the solvent) is 100% by mass. When it is 1.0 mass% or more and 25.0 mass% or less is preferable, and 2.0 mass% or more and 15.0 mass% or less 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 based on 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 prepreg obtained 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 resin such as cyclohexidiene bisphenol type epoxy resin); phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol-based ethane type novolac type epoxy resin, no 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; An adamantane type epoxy resin; a fluorene type epoxy resin etc. are mentioned.

  Among the epoxy resins (D), one of them may be used alone, or two or more may be used in combination, or one or more of them may be used in combination with their prepolymers. .

  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 two or more selected from the group consisting of epoxy resins are more preferable.

  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.

  Among the epoxy resins (D), one of them may be used alone, or two or more may be used in combination, or one or more of them may be used in combination with their prepolymers. Good.

  Among these epoxy resins (D), aralkyl type epoxy resins are particularly preferable. Thereby, the moisture absorption solder heat resistance and the 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, Mw 300 or more is preferable and especially Mw 800 or more is preferable. It can suppress that tackiness arises in a prepreg as Mw is more than the said lower limit. Although the upper limit of Mw is not specifically limited, Mw 20,000 or less is preferable, and Mw 15,000 or less is particularly preferable. When Mw is less than or equal to the above upper limit, the impregnating property to the fiber base material is improved at the time of preparation of the prepreg, and a more uniform prepreg can be obtained. The Mw of the epoxy resin can be measured, for example, by GPC.

  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). It is preferable that they are 1 mass% or more and 50 mass% or less, when the whole quantity of the component except these is 100 mass%. 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. You may

  It is preferable that the resin composition (P) according to the present embodiment further includes an inorganic filler (C). Thereby, storage elastic modulus E 'of the hardened | cured material of the prepreg obtained and a resin substrate can be improved. Furthermore, the linear expansion coefficient of the obtained insulating layer 301 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; and 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. It can suppress that the viscosity of a varnish becomes high as the average particle diameter of an inorganic filler (C) is more than the said lower limit, and the workability at the time of preparation of a prepreg can be improved. The average particle size 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 still more preferably 1.0 μm or less. When the average particle diameter of the inorganic filler (C) is equal to or less than the above upper limit, phenomena such as sedimentation of the inorganic filler (C) can be suppressed in the varnish, and a more uniform resin layer can be obtained. In addition, when the circuit dimension L / S of the printed wiring board is less than 20/20 μm, it is possible to suppress the influence of the insulation between the wires.
The average particle diameter of the inorganic filler (C) is measured, for example, by using a laser diffraction particle size distribution analyzer (LA-500, manufactured by HORIBA, Inc.) on a volume basis, and the median diameter (D ₅₀ ) of the particles. 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. Further, inorganic fillers having a monodispersed and / or polydispersed average particle size may be used in combination of one or more kinds.

  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 the inorganic filler (C) can be further 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 is preferable, and 60.0 mass% or more and 80.0 mass% or less is 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.

The resin composition (P) preferably further contains 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.
As the low stress material (E), for example, (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. Minutes 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 Acrylic monomer having an epoxy group in the inside; allyl group-containing acrylic monomer having an allyl group in the molecule such as allyl acrylate and allyl methacrylate; γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyl Silane group-containing acrylic monomer having hydrolyzable silyl group in molecule such as oxypropyltriethoxysilane; benzotriazole such as 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole Examples thereof include UV-absorbing acrylic monomers having a UV-absorbing group.

  In addition, monomers other than the said acryl-type monomer may be used as a monomer component for the said (meth) acryl-type block copolymer. Examples of monomers other than the above acrylic monomers 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.

  The above (meth) acrylic block copolymer is not particularly limited, but, for example, a diblock copolymer consisting of two polymer blocks, a triblock copolymer consisting of three polymer blocks, four or more And multi-block copolymers composed of polymer blocks of

  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) etc. are mentioned.

  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.

  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 increase in elastic modulus due to heat history hardly occurs.

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

  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 rubber particles include staphyroid AC3832, AC3816N (trade name, manufactured by Ganz Chemical Co., Ltd.), and metabrene KW-4426 (trade name, 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 diameter 0.5 μm, manufactured by JSR Corporation) and the like. As a specific example of an acrylic rubber particle, metabrene W300A (average particle diameter 0.1 micrometer), W450A (average particle diameter 0.2 micrometer) (made by Mitsubishi Rayon Co., Ltd.) etc. are mentioned.

  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. It 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. It can be done.

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

  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. Among these, imidazole compounds are preferable. 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; secondary phosphines such as dimethyl phosphine and dialkyl phosphine such as diethyl phosphine, diphenyl phosphine, methyl phenyl phosphine, and ethyl phenyl phosphine. Trimethyl phosphine, triethyl phosphine, trialkyl phosphine, trialkyl phosphine such as trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, alkyl diphenyl phosphine, dialkyl phenyl phosphine, tribenzyl phosphine, tri tolyl phosphine, tri-p-styryl phosphine , Tris (2,6-dimethoxyphenyl) phosphine, tri-4-methylphen Le phosphine, tri-4-methoxyphenyl phosphine, tertiary phosphines such as tri-2-cyanoethyl phosphine, and the like. Among these, tertiary phosphines are preferably used.

Moreover, as a compound which has a phosphonium salt, the compound which has tetraphenyl phosphonium salt, an alkyl triphenyl phosphonium salt etc. is mentioned, Specifically, tetraphenyl phosphonium thiocyanate, tetraphenyl phosphonium tetra-p-methylphenyl borate, butyl Triphenyl phosphonium thiocyanate etc. are mentioned.

  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 directly added at the time of preparation of the resin composition (P), or may be previously added 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 cured product of the obtained prepreg and the 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 between the fiber base material or the inorganic filler (C) and each resin can be enhanced, and the heat resistance of the cured product of the obtained prepreg and the resin substrate can be further improved.

  Although various things can be used as a silane coupling agent, For example, an epoxysilane, an aminosilane, an alkylsilane, a ureidosilane, a mercaptosilane, a vinylsilane etc. are mentioned.

  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 one or a combination of two 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 of the resin composition (P) (that is, the component excluding the solvent) is 100% by mass. When it is, 0.01 mass% or more and 1 mass% or less are preferable, and 0.05 mass% or more and 0.5 mass% or less are more preferable.
An inorganic filler (C) can fully be coat | covered as content of a coupling agent is more than the said lower limit, and the heat resistance of the hardened | cured material of the prepreg obtained and a 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-mentioned 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, perinone, anthraquinone, indigoid, oxazine, quinacridone, benzimidazolone, biolanthrone, 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, N-methyl pyrrolidone, etc., using various mixers such as ultrasonic dispersion type, high pressure collision type dispersion type, high speed rotational dispersion type, bead mill type, high speed shear dispersion type, rotation revolution type dispersion type It can be dissolved, mixed and stirred to obtain resin varnish (I).
The solid content of the resin varnish (I) is not particularly limited, but is preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass. 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, for example, as follows.
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 proportion of the maleimide compound (A) is 5.0% by mass or more and 20.0% by mass or less and the proportion 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.

  Below, the prepreg in this embodiment is demonstrated.

  A prepreg is used to form 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.

Moreover, a resin substrate is used in order to form the insulating layer of a 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 using a prepreg to form an insulating layer in a core layer of a printed wiring board, for example, two or more prepregs are stacked, and the obtained laminate is heated and 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 a resin substrate obtained by heat and pressure molding at a pressure of 4 MPa and a temperature of 230 ° C. for 2 hours is preferably 250 ° C. or more, more preferably 260 ° C. or more, still more preferably 270 It is at least 280 ° C, particularly preferably at least 280 ° C. For the upper limit, for example, 400 ° C. or less is preferable. The glass transition temperature can be measured using a dynamic viscoelastic analyzer (DMA).
In the cured product or the resin substrate, when the glass transition temperature by dynamic viscoelasticity measurement satisfies the above range, the rigidity of the obtained printed wiring board is enhanced, and the warpage of the printed wiring board at the time of mounting 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 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 base, 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 storage elastic modulus E ′ ₃₀ at 30 ° C. of the obtained cured product or resin substrate is 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.
In the cured product or resin substrate, when the storage elastic modulus E ′ ₃₀ at 30 ° C. satisfies the above range, 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 Warpage 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 resulting cured product or ₃₀ the ratio of 'the storage modulus E at 30 ° C. for _250' the storage modulus E at 250 ° C. of the resin substrate (E _'30 / E' ₂₅₀₎ is 1.05 or more 1.75 or less Is preferred.
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. Thus, even if a large temperature change occurs, deformation or the like of the insulating layer is unlikely to occur, and displacement of the semiconductor element with respect to the printed wiring board can be suppressed, and connection reliability between the semiconductor element and the printed wiring board is further enhanced. Can do.

To achieve such a storage modulus E _'30 and E' ₃₀ / E _'250, the 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 enhancing 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.degree. 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 above-mentioned cured product or resin substrate, when the average linear expansion coefficient α ₁ satisfies the above range, the linear expansion coefficient between the circuit layer and the insulating layer is obtained even if a large change occurs in the environmental temperature in the obtained printed wiring board 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 It is possible to reduce the resulting stress. 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 enhancing 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.degree. 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 heat pressure molding 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.
In the above-mentioned cured product or resin substrate, in the printed wiring board obtained when α ₂ / α ₁ satisfies the above range, the linear expansion coefficient difference between the circuit layer and the insulating layer even if a large change occurs in the environmental temperature It is possible to reduce the change in stress that occurs due to 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, in the above-mentioned cured product or resin substrate, in the semiconductor device obtained when α ₂ / α ₁ satisfies the above range, even if a large change occurs in the environmental temperature, linear expansion between the printed wiring substrate and the semiconductor element It is possible to reduce the change in stress that occurs due to the difference in coefficients. 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 .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 expansion coefficient difference 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 an average linear expansion coefficient α ₁ , α ₂ or α ₂ / α ₁ , the maleimide compound (A), the benzoxazine compound (B), the inorganic filler (C), the epoxy resin (D) It is important to appropriately control the types and blending amounts of the low stress material (E), the fiber substrate, the curing accelerator, etc., and the method of producing the prepreg.

Further, from the viewpoint of further enhancing the connection reliability between the semiconductor element and the printed wiring board, for example, in a cured product or a resin substrate obtained by heating and pressing a prepreg at a pressure of 4 MPa and a temperature of 230 ° C. for 2 hours. When performing thermomechanical analysis measurement which comprises a process of raising the temperature from 30 ° C to 260 ° C at 10 ° C / min and a process of holding it at 260 ° C for 1 hour using a thermomechanical analyzer. 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. It is more preferable that Although it does not specifically limit about a lower limit, For example, it can be 0.00% or more.
The longitudinal direction of the cured product refers to the transport direction of the prepreg (so-called MD).
In the cured product or the resin substrate, when the dimensional shrinkage ratio satisfies the above range, in the obtained semiconductor device, the stress generated due to the shrinkage of the insulating layer in the printed wiring substrate when exposed to a high temperature is reduced can do. As a result, the adhesion between the insulating layer and the circuit layer can be maintained even if the temperature change is severed for a long time, so that the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be 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 dimensional shrinkage, maleimide compound (A), benzoxazine compound (B), inorganic filler (C), epoxy resin (D), low stress material (E), fiber base material, It is important to appropriately control the type and amount of the curing accelerator and the like, the method of producing the prepreg, 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 area of both front and back sides of the cured product)] that the amount of film reduction defined by × 100 is 1.2 g / m ² or less preferable.
<Conditions>
Cured product by immersing the cured product in 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

  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 film reduction, a maleimide compound (A), a benzoxazine compound (B), an inorganic filler (C), an epoxy resin (D), a low stress material (E), a fiber substrate, It is important to appropriately control the type and amount of the curing accelerator and the like, the method of producing the prepreg, 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. In the metal-clad laminate 200, a metal foil 105 is provided on one side or both sides of a cured product of a prepreg (insulating layer 301) or a cured product of a laminate obtained by stacking two or more prepregs (insulating layer 301). 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 composition 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 substrate is dipped in the resin varnish. Method of applying the above resin varnish to a fiber substrate by various coaters, method of spraying the above resin varnish onto a fiber substrate by spraying, resin layer (P) comprising the resin composition (P) from both sides of the fiber substrate And a method of laminating a fiber substrate.

Next, a method for manufacturing the metal-clad laminate 200 using the prepreg obtained above will be described. The manufacturing method of the metal-clad laminated board 200 using a prepreg is as follows, for example.
Metal foils 105 are stacked on both upper and lower sides or one side of the outer side of a laminate in which two or more prepregs or prepregs are stacked, and these are joined under high vacuum conditions using a laminator device or a Becquerel device, or directly outside the prepreg. A metal foil 105 is stacked on both the upper and lower sides or one side. 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 heat and pressure molding 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 a high pressure of 2.5 MPa or more and 5 MPa or less.

  In addition, after the heat and pressure molding, post curing may be performed in a thermostatic chamber or the like, if necessary. The temperature for post-curing is preferably 150 ° C. or more and 300 ° C. or less, more preferably 250 ° C. or more and 300 ° C. or less.

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

  Hereinafter, each material used when manufacturing a prepreg, the metal-clad laminated board 200, and a resin substrate is demonstrated 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 And polyester-based resin fibers such as aromatic polyester resin fibers and wholly aromatic polyester resin fibers; synthetic fiber base materials composed of woven or non-woven fabric mainly composed of polyimide resin fibers and fluorocarbon resin 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 base material is preferable. Thus, a resin substrate with low water absorption, high strength and low thermal expansion can be obtained.

The thickness of the fiber substrate is not particularly limited, but is preferably 5 μm to 150 μm, more preferably 10 μm to 100 μm, and still more preferably 12 μm to 90 μm. 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 suitably 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 applying an electroless metal plating film 308 on the metal foil 105 or the insulating layer 301, the non-circuit forming portion is protected by a plating resist, and an electrolytic metal plating layer 309 is applied by electrolytic plating to remove the plating resist and flash etching. The metal layer 303 is formed on the metal foil 105 or the insulating layer 301 by the removal of the electroless metal plating film 308 by the

  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 fine wiring is used, the insulation reliability between the wirings is reduced. 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, either a resin film or a prepreg. Among them, the prepreg is a sheet-like material and is excellent in various characteristics such as dielectric characteristics, mechanical and electrical connection reliability under high temperature and humidity, and is suitable for manufacturing a buildup layer 317 for a printed wiring board. preferable.
As the prepreg, the above-mentioned prepreg 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.

  Subsequently, an example of a method of 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 an etching process.

Next, a via hole 307 is formed in the insulating layer 301. The via hole 307 can be formed using, for example, a drill or laser irradiation. Examples of the laser used for laser irradiation include an excimer laser, a UV laser, and a carbon dioxide gas laser. The resin residue or the like after the formation of 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). The details will be described below.

  First, the electroless metal plating film 308 is formed in the surface of the metal foil 105 or the insulating layer 301 or in the via hole 307 by using the electroless plating method, and conduction on both sides 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, and for example, noble metal ions and palladium colloid can be used. Subsequently, an electroless metal plating film 308 is formed by electroless plating using the catalyst nuclei as nuclei. 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. Heat treatment at 120 to 180 ° C. is particularly preferable in that it can form a film capable of suppressing oxidation. 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. The 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. The electroplating process is not particularly limited, but any known method used for a general printed wiring board can be used. For example, a current can be applied to the plating solution while being immersed in a plating solution such as copper sulfate. Methods such as streaming 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 plated 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 process can be performed, for example, by etching using an etching solution 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.

  Thus, the printed wiring board 300 of the present embodiment is obtained.

  Subsequently, 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 in the present embodiment. The printed wiring board 300 can be used for a semiconductor device 400 as shown in FIGS. 4 and 5. The method of manufacturing the semiconductor device 400 is not particularly limited, and for example, there are the following methods.

  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. Then, the solder resist layer 401 is laminated on both sides or one side of the printed wiring board 300 as necessary.

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

  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.

（前記式（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）
２． １．に記載のプリント配線基板用樹脂組成物において、前記マレイミド化合物（Ａ）が前記ビスマレイミド化合物（Ａ１）とは異なる種類のマレイミド化合物（Ａ２）をさらに含むプリント配線基板用樹脂組成物。
３． ２．に記載のプリント配線基板用樹脂組成物において、前記マレイミド化合物（Ａ２）が下記式（１）により示されるマレイミド化合物および１，６'−ビスマレイミド−（２，２，４−トリメチル）ヘキサンから選択される少なくとも一種を含むプリント配線基板用樹脂組成物。

（前記式（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）

（前記式（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）
４． １．乃至３．いずれかに記載のプリント配線基板用樹脂組成物において、ベンゾオキサジン化合物（Ｂ）をさらに含むプリント配線基板用樹脂組成物。
５． ４．に記載のプリント配線基板用樹脂組成物において、前記ベンゾオキサジン化合物（Ｂ）は下記式（２）により示される化合物、下記式（３）により示される化合物から選択される一種または二種以上を含むプリント配線基板用樹脂組成物。

（前記式（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、前記式（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１〜６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）

（前記式（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、前記式（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１〜６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）
６． ５．に記載のプリント配線基板用樹脂組成物において、前記ベンゾオキサジン化合物（Ｂ）が下記式（２−１）により示される化合物、下記式（２−２）により示される化合物、下記式（２−３）により示される化合物、下記式（３−１）により示される化合物、下記式（３−２）により示される化合物および下記式（３−３）により示される化合物から選択される一種または二種以上を含むプリント配線基板用樹脂組成物。

（前記式（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）
７． ４．乃至６．いずれかに記載のプリント配線基板用樹脂組成物において、前記マレイミド化合物（Ａ）の含有量が、前記マレイミド化合物（Ａ）および前記ベンゾオキサジン化合物（Ｂ）の合計１００質量％に対して３５質量％以上８０質量％以下であるプリント配線基板用樹脂組成物。
８． １．乃至７．いずれかに記載のプリント配線基板用樹脂組成物において、低応力材（Ｅ）をさらに含むプリント配線基板用樹脂組成物。
９． ８．に記載のプリント配線基板用樹脂組成物において、前記低応力材（Ｅ）が（メタ）アクリル系ブロック共重合体；シリコーン化合物；カルボキシル基、アミノ基、ビニルアクリレート基またはエポキシ基により変性されたアクリロニトリル・ブタジエンゴム；脂肪族エポキシ樹脂；およびゴム粒子から選択される一種または二種以上を含むプリント配線基板用樹脂組成物。
１０． １．乃至９．いずれかに記載のプリント配線基板用樹脂組成物において、無機充填材（Ｃ）をさらに含むプリント配線基板用樹脂組成物。
１１． １０．に記載のプリント配線基板用樹脂組成物において、前記無機充填材（Ｃ）がタルク、アルミナ、ガラス、シリカ、マイカ、ベーマイト、水酸化アルミニウム、および水酸化マグネシウムから選択される一種または二種以上を含むプリント配線基板用樹脂組成物。
１２． １０．または１１．に記載のプリント配線基板用樹脂組成物において、前記無機充填材（Ｃ）の含有量が、前記プリント配線基板用樹脂組成物の全固形分１００質量％に対し、５０質量％以上８５質量％以下であるプリント配線基板用樹脂組成物。
１３． １．乃至１２．いずれかに記載のプリント配線基板用樹脂組成物において、エポキシ樹脂（Ｄ）をさらに含むプリント配線基板用樹脂組成物。
１４． １３．に記載のプリント配線基板用樹脂組成物において、前記エポキシ樹脂（Ｄ）の含有量が、前記プリント配線基板用樹脂組成物中の前記無機充填材（Ｃ）を除く成分の全量を１００質量％としたとき、１質量％以上５０質量％以下であるプリント配線基板用樹脂組成物。
１５． １．乃至１４．いずれかに記載のプリント配線基板用樹脂組成物を繊維基材に含浸してなるプリプレグ。
１６． １５．に記載のプリプレグにおいて、昇温速度５℃／ｍｉｎ、周波数１Ｈｚの条件での動的粘弾性測定により測定される、当該プリプレグを２３０℃、２時間加熱処理して得られる硬化物のガラス転移温度が２５０℃以上であるプリプレグ。
１７． １５．または１６．に記載のプリプレグにおいて、当該プリプレグを２３０℃、２時間加熱処理して得られる硬化物の２５０℃での貯蔵弾性率Ｅ' _２５０ に対する３０℃での貯蔵弾性率Ｅ' _３０ の比（Ｅ' _３０ ／Ｅ' _２５０ ）が、１．０５以上１．７５以下であるプリプレグ。
１８． １５．乃至１７．いずれかに記載のプリプレグにおいて、当該プリプレグを２３０℃、２時間加熱処理して得られる硬化物の面内方向における、５０℃から１５０℃の範囲において算出した平均線膨張係数α _１ に対する１５０℃から２５０℃の範囲において算出した平均線膨張係数α _２ の比（α _２ ／α _１ ）が、０．７以上２．０以下であるプリプレグ。
１９． １５．乃至１８．いずれかに記載のプリプレグにおいて、当該プリプレグを２３０℃、２時間加熱処理して得られる硬化物に対し、熱機械分析装置を用いて、３０℃から２６０℃まで１０℃／ｍｉｎで昇温する過程と、２６０℃で１時間保持する過程とからなる熱機械分析測定を行ったとき、前記熱機械分析測定前の前記硬化物の縦方向の長さを基準長Ｌ _０ とし、前記硬化物の前記基準長Ｌ _０ からの最大の熱膨張量をＬ _１ とし、前記硬化物を２６０℃で１時間保持したときの前記基準長Ｌ _０ からの熱膨張量をＬ _２ とした場合、１００×（Ｌ _１ −Ｌ _２ ）／Ｌ _０ で示される寸法収縮率が０．１５％以下であるプリプレグ。
２０． １５．乃至１９．いずれかに記載のプリプレグにおいて、当該プリプレグを２３０℃、２時間加熱処理して得られる硬化物の質量を第１の質量とし、当該硬化物を下記条件で処理した後の硬化物の質量を第２の質量としたとき、
［｛（第１の質量）−（第２の質量）｝／（当該硬化物の表裏両面の面積の和）］×１００で定義される減膜量が１．２ｇ／ｍ ^２ 以下であるプリプレグ。
＜条件＞
前記硬化物を３ｇ／Ｌ水酸化ナトリウム溶液（溶媒：ジエチレングリコールモノブチルエーテル１１．１体積％、エチレングリコール３．６体積％、純水８５．３体積％）に６０℃、５分間浸漬することにより前記硬化物を膨潤させ、次いで、膨潤した前記硬化物を粗化処理水溶液（過マンガン酸ナトリウム６０ｇ／Ｌ、水酸化ナトリウム４５ｇ／Ｌ）に８０℃、５分間浸漬することにより前記硬化物を粗化処理し、次いで、粗化処理した前記硬化物を中和液（９８質量％硫酸５．０体積％、硫酸ヒドロキシルアミン０．８体積％、純水９４．２体積％）に４０℃、５分間浸漬することにより前記硬化物を中和する
２１． １５．乃至２０．いずれかに記載のプリプレグにおいて、前記繊維基材がＥガラス、Ｓガラス、Ｄガラス、Ｔガラス、ＮＥガラス、ＵＴガラス、Ｌガラス、ＨＰガラスおよび石英ガラスから選ばれる一種または二種以上のガラスにより形成されたガラス繊維基材であるプリプレグ。
２２． １５．乃至２１．いずれかに記載のプリプレグにおいて、当該プリプレグの厚みが２０μｍ以上２２０μｍ以下であるプリプレグ。
２３． １５．乃至２２．いずれかに記載のプリプレグの硬化物を含む樹脂基板。
２４． １５．乃至２２．いずれかに記載のプリプレグの硬化物または前記プリプレグを２枚以上重ね合わせた積層体の硬化物の片面または両面に金属箔が設けられている金属張積層板。
２５． ２３．に記載の樹脂基板または２４．に記載の金属張積層板を回路加工して得られるものであり、１層又は２層以上の回路層が設けられているプリント配線基板。
２６． ２５．に記載のプリント配線基板の前記回路層上に半導体素子を搭載した半導体装置。 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, examples of the embodiment will be additionally described.
1. 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 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 an organic group, n Is an integer from 1 to 10.
2. 1. The resin composition for printed wiring boards according to claim 1, wherein the maleimide compound (A) further comprises a maleimide compound (A2) of a type different from the bismaleimide compound (A1).
3. 2. In the resin composition for printed wiring boards described in 1), the maleimide compound (A2) is selected from a maleimide compound represented by the following formula (1) and 1,6′-bismaleimide- (2,2,4-trimethyl) hexane A printed wiring board resin composition comprising at least one of the above.

(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.)
4. 1. To 3. The resin composition for printed wiring boards according to any one of the above, further comprising a benzoxazine compound (B).
5. 4. In the resin composition for printed wiring board according to the above, the benzoxazine compound (B) contains one or more selected from a compound represented by the following formula (2) and a compound represented by the following formula (3) Resin composition for printed wiring boards.

(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)
6). 5. In the resin composition for printed wiring boards described in 1), the benzoxazine compound (B) is a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), and the following formula (2-3). Or one or more selected from a compound represented by the following formula (3-1), a compound represented by the following formula (3-2), and a compound represented by the following formula (3-3) A resin composition for printed wiring boards comprising:

(In said Formula (2-3), R is respectively independently a C1-C4 hydrocarbon group.)
7). 4. To 6. In the resin composition for printed wiring boards according to any one of the above, the content of the maleimide compound (A) is 35% by mass with respect to 100% by mass in total of the maleimide compound (A) and the benzoxazine compound (B). The resin composition for printed wiring boards which is 80 mass% or less.
8). 1. To 7. The resin composition for printed wiring boards according to any one of the above, further comprising a low stress material (E).
9. 8). The acrylonitrile in which the low stress material (E) is modified with a (meth) acrylic block copolymer; a silicone compound; a carboxyl group, an amino group, a vinyl acrylate group, or an epoxy group. A resin composition for a printed wiring board comprising one or more selected from butadiene rubber; aliphatic epoxy resin; and rubber particles.
10. 1. To 9. The resin composition for a printed wiring board according to any one of the above, further comprising an inorganic filler (C).
11. 10. The resin composition for printed wiring board according to claim 1, wherein the inorganic filler (C) is one or more selected from talc, alumina, glass, silica, mica, boehmite, aluminum hydroxide and magnesium hydroxide. And a resin composition for printed wiring board.
12 10. Or 11. In the resin composition for printed wiring board according to claim 5, the content of the inorganic filler (C) is 50% by mass or more and 85% by mass or less with respect to 100% by mass of the total solid content of the resin composition for printed wiring board A resin composition for printed wiring boards.
13. 1. To 12. The resin composition for printed wiring boards according to any one of the above, further comprising an epoxy resin (D).
14 13. In the resin composition for a printed wiring board according to claim 1, the total content of components excluding the inorganic filler (C) in the resin composition for a printed wiring board is 100% by mass with the content of the epoxy resin (D) When printed, a resin composition for a printed wiring board that is 1% by mass or more and 50% by mass or less.
15. 1. To 14. A prepreg obtained by impregnating a fiber base material with the resin composition for a printed wiring board according to any one of the above.
16. 15. The glass transition temperature of a cured product obtained by heat-treating the prepreg for 2 hours at 230 ° C., which is measured by dynamic viscoelasticity measurement under conditions of a temperature elevation rate of 5 ° C./min and a frequency of 1 Hz. Prepreg having a temperature of 250 ° C. or higher.
17. 15. Or 16. In prepreg according to, the prepreg 230 ° C., 2 hours of heat treatment was at 250 ° C. of the cured product obtained by ₃₀ the ratio of 'the storage modulus E at 30 ° C. for _250' the storage modulus E of the (E _'30 / E ′ ₂₅₀ ) is 1.05 or more and 1.75 or less.
18. 15. To 17. In any of the prepregs, from 150 ° C. to an average linear expansion coefficient α ₁ calculated in the range of 50 ° C. to 150 ° C. in the in-plane direction of a cured product obtained by heat treating the prepreg for 2 hours at 230 ° C. A prepreg having a ratio (α ₂ / α ₁ ) of an average linear expansion coefficient α ₂ calculated in a range of 250 ° C. of 0.7 or more and 2.0 or less.
19. 15. To 18. The process of raising the temperature of the cured product obtained by heat treating the prepreg for 2 hours at 230 ° C. from 10 ° C. to 260 ° C. at 10 ° C./min using any of the prepregs described in any of the above. And a process of holding at 260 ° C. for 1 hour, the length in the longitudinal direction of the cured product before the thermal mechanical analysis measurement is taken as a reference length L _0, and If the maximum heat expansion amount from the reference length L ₀ and L _1, the thermal expansion amount from the reference length L ₀ when the cured product was held for 1 hour at 260 ° C. was L _2, 100 × (L A prepreg having a dimensional shrinkage represented by ₁₋ L ₂ ) / L ₀ of 0.15% or less.
20. 15. Thru 19. In any of the prepregs described above, the mass of a cured product obtained by heat-treating the prepreg at 230 ° C. for 2 hours is taken as a first mass, and the mass of the cured product after the cured product is treated under the following conditions is Assuming a mass of 2,
A prepreg having a film reduction amount of 1.2 g / m ² or less defined by [{(first mass) − (second mass)} / (sum of areas of both surfaces of the cured product) × 100 .
<Conditions>
The cured product is immersed 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 roughened aqueous solution (60 g / L of sodium permanganate, 45 g / L of sodium hydroxide) at 80 ° C. for 5 minutes. Treated and then roughened the cured product in 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 immersion
21. 15. To 20. In the prepreg according to any of the above, the fiber base material is at least one glass selected from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass and quartz glass A prepreg that is a formed glass fiber base material.
22. 15. Thru 21. The prepreg described in any one of the above, wherein the thickness of the prepreg is 20 μm or more and 220 μm or less.
23. 15. Thru 22. The resin substrate containing the hardened | cured material of the prepreg in any one.
24. 15. Thru 22. The metal-clad laminate in which metal foil is provided in the single side | surface or both surfaces of the hardened | cured material of the prepreg as described in any one or the hardened | cured material of the laminated body which piled up 2 or more sheets of said prepregs.
25. 23. 24. The resin substrate described in or 24. A printed wiring board obtained by subjecting the metal-clad laminate described in 1. to a circuit to one or more circuit layers.
26. 25. A semiconductor device in which a semiconductor element is mounted on the circuit layer of the printed wiring board according to 1.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these. In the examples, parts represent parts by mass unless otherwise specified. Further, each thickness is represented by an 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: In the formula (1), a compound in which n ₁ is 0 or more and 3 or less, X ₁ is a group represented by “—CH ₂ —”, a is 0, b is 0 (BMI-2300, Daiwa 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)
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 (three-dimensional crosslinked silicone resin containing epoxy group and phenyl group, manufactured by Toray Dow Corning, AY 42-119)
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, SG-P 3 Mw 4)

Hardening 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, the production of a 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)
Glass woven fabric (cross type # 2118, T glass, basis weight 114 g / m ² ) is impregnated with resin varnish 1 with a coating apparatus, and dried for 10 minutes with a hot air drying apparatus at 140 ° C. I got P1).

(Prepreg 2 to 19)
Prepregs 2 to 19 were manufactured in the same manner as Prepreg 1 except that the type of resin varnish was 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 Ultra-thin copper foil (Microsyn Ex, 2.0 μm, manufactured by Mitsui Mining & Smelting Co., Ltd.) is laminated on both sides of the prepreg 1, and heat compression molding is performed 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, the substrate is immersed for 5 minutes in a 60 ° C. swelling solution (Atotech Japan Co., Ltd., SWELLING DIP SECUREGANT P), and further immersed for 2 minutes in an 80 ° C. potassium permanganate aqueous solution (Atotech Japan Co., Ltd., concentrate compact CP) After that, it was neutralized to perform desmear treatment in the through holes. 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.

  Moreover, each following evaluation was performed about the resin substrate obtained by each Example and the comparative example. 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 exhibits 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 cured product of the obtained prepreg, the storage elastic modulus is measured at 30 ° C. and 250 ° C. at a heating rate of 5 ° C./min, at a frequency of 1 Hz, and storage elastic modulus E ′ _{30 at 30} ° C. Storage elastic modulus E ' ₂₅₀ , E' ₃₀ / E ' ₂₅₀ were calculated.

(3) Dimensional Shrinkage A 4 mm × 15 mm test piece 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 hardened 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 L ₁ from the reference length L ₀ of the cured product of the prepreg and the thermal expansion L ₂ from the reference length L ₀ when the cured product of the prepreg was held at 260 ° C. for 1 hour was 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 × 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 hardened 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 The thermal mechanical analysis (TMA) was measured 2 cycles under the conditions of the mode. 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 expansion coefficient employ | adopted the value of the 2nd cycle.

(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 hardened prepreg. Then, the mass after drying for 1 hour at 120 ° C. of the cured product of the obtained prepreg is taken as the 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 the second mass is used, the amount of film reduction defined by [{(first mass) − (second mass)} / (sum of areas of both surfaces of the cured product) × 100 was calculated. .
<Conditions>
Cured product by immersing the cured product in 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 buildup 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. The resistance value was 10 ⁶ Ω or less. 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)
X: 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. . 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. The resistance value was 10 ⁶ Ω or less. Evaluation criteria are as follows.
:: No failure for 500 hours or more (good)
○: Failure occurred in less than 200 to 500 hours (substantially no problem)
:: Failure occurred in less than 200 hours (substantially unusable)
X: Failure in less than 100 hours (not available)

(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, the semiconductor device was manufactured by dicing into 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 downward in the sample chamber of the above-mentioned measuring machine, displacement in the height direction was measured, and the largest value of the displacement difference was taken as the amount of warpage. 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) are treated at 85 ° C. and 85% conditions for 168 hours, and then treated three times in an IR reflow furnace (peak temperature: 260 ° C.) to the air 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 Have problems in practice

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 Build-up layer 400 Semiconductor device 401 Solder resist layer 407 Semiconductor Element 410 Solder bump 413 Sealing material

Claims (24)

A thermosetting resin composition used for forming an insulating layer in a printed wiring board,
A maleimide compound (A) and a benzoxazine compound (B) ,
The maleimide compound (A) contains at least one bismaleimide compound (A1) selected from a compound represented by the following formula (a) and a compound represented by the formula (a3) ,
A resin composition for a printed wiring board , wherein the benzoxazine compound (B) contains at least one selected from a compound represented by the following formula (2) and a compound represented by the following formula (3) .

(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 an organic group, n Is an integer from 1 to 10.

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

(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 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 according to claim 1 ,
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 said Formula (2-3), R is respectively independently a C1-C4 hydrocarbon group.) In the resin composition for printed wiring boards as described in any one of Claims 1 to 4 ,
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 according to any one of claims 1 to 5 ,
The resin composition for printed wiring boards which further contains a low stress material (E). In the resin composition for printed wiring boards according to claim 6 ,
(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 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 according to any one of claims 1 to 7 ,
The resin composition for printed wiring boards which further contains an inorganic filler (C). In the resin composition for printed wiring boards according to claim 8 ,
The resin composition for printed wiring boards, 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 8 or 9 ,
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. The resin composition for a printed wiring board according to any one of claims 1 to 10 ,
A printed wiring board resin composition further comprising an epoxy resin (D). In the resin composition for printed wiring boards according to claim 11 ,
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 resin composition for a printed wiring board. A prepreg obtained by impregnating a fiber base material with the resin composition for a printed wiring board according to any one of claims 1 to 12 . In the prepreg according to claim 13 ,
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. In the prepreg according to claim 13 or 14 ,
The prepreg 230 ° C., 2 hours of heat treatment to ₃₀ ratio of 'the storage modulus E at 30 ° C. for _250' the storage modulus E at 250 ° C. of the cured product obtained (E _'30 / E' ₂₅₀₎ is , A prepreg which is 1.05 or more and 1.75 or less. The prepreg according to any one of claims 13 to 15 ,
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 treating the prepreg for 2 hours at 230 ° C. 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 13 to 16 ,
With respect to a cured product obtained by heat treating the prepreg at 230 ° C. for 2 hours,
Using a thermomechanical analyzer
When a thermomechanical analysis measurement is performed comprising a process of raising the temperature from 30 ° C. to 260 ° C. at 10 ° C./min and a process of holding at 260 ° C. for 1 hour, 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. If the thermal expansion amount was L _2,
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 13 to 17 ,
The mass of a cured product obtained by heat-treating the prepreg at 230 ° C. for 2 hours is taken as a first mass, and the mass of the cured product after the cured product is treated under the following conditions is taken as a 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>
The cured product is immersed 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 immersion The prepreg according to any one of claims 13 to 18 ,
The fiber substrate is a glass fiber substrate formed of one or two or more glasses selected from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass and quartz glass There is a prepreg. The prepreg according to any one of claims 13 to 19 ,
The prepreg whose thickness of the said prepreg is 20 micrometers or more and 220 micrometers or less. A resin substrate comprising the cured product of the prepreg according to any one of claims 13 to 20. A metal-clad laminate in which a metal foil is provided on one side or both sides of a cured product of the prepreg according to any one of claims 13 to 20 or a cured product of a laminate obtained by superimposing two or more prepregs. A printed wiring board obtained by circuit-processing the resin substrate according to claim 21 or the metal-clad laminate according to claim 22 and provided with one or more circuit layers. The semiconductor device which mounts the semiconductor element on the said circuit layer of the printed wiring board of Claim 23 .

Images