WO2017170643A1

WO2017170643A1 - Thermosetting resin composition, resin film with carrier, pre-preg, metal-clad laminate sheet, resin substrate, printed wiring substrate and semiconductor device

Info

Publication number: WO2017170643A1
Application number: PCT/JP2017/012819
Authority: WO
Inventors: 大東　範行
Original assignee: 住友ベークライト株式会社
Priority date: 2016-03-31
Filing date: 2017-03-29
Publication date: 2017-10-05
Also published as: JPWO2017170643A1; TW201808622A

Abstract

This thermosetting resin composition is used to form an insulating layer on a printed wiring substrate, wherein the thermosetting resin composition includes: a prescribed benzoxazine compound that contains a group having an unsaturated double bond; a thermosetting resin that contains at least one of a malemide compound, an epoxy resin and a cyanate resin; and an inorganic filler. In addition, the benzoxazine compound contains a C3-C14 alkenyl group as the group that has an unsaturated double bond. Furthermore, the group that has an unsaturated double bond is preferably an allyl group.

Description

Thermosetting resin composition, resin film with carrier, prepreg, metal-clad laminate, resin substrate, printed wiring board, and semiconductor device

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

In the past, various developments have been made on sealing resin compositions from the viewpoint of heat resistance. As this type of technology, for example, a sealing resin composition described in Patent Document 1 can be mentioned. This document describes that heat resistance can be improved by using a bismaleimide compound and a Pd-type benzoxazine as a sealing resin composition (paragraph 0040 of Patent Document 1, Examples). ).

JP 2012-97207 A

However, in the recent semiconductor package manufacturing process, the area has been increasing. In light of such a development environment, the present inventors have examined, in the cured product of the sealing resin composition described in the above literature, there is room for improvement in terms of warping of the printed wiring board during the manufacturing process. Turned out to be.

The present inventor further examined the thermosetting resin composition used for forming the insulating layer in the printed wiring board, and focused on the variety of reactions according to the functional group of the benzoxazine compound. As a result of examination based on such points of view, it was found that the curing characteristics of the thermosetting resin composition can be improved by using a benzoxazine compound containing a group having an unsaturated double bond as a functional group. did.

As a result of intensive studies based on such findings, a benzoxazine compound containing a group having an unsaturated double bond and a thermosetting resin containing at least one of a maleimide compound, an epoxy resin and a cyanate resin are obtained. It was found that the linear expansion coefficient of the obtained cured product can be lowered by using in combination. And when the linear expansion coefficient of the hardened | cured material obtained becomes low, it discovered that the curvature of the printed wiring board in a manufacturing process could be suppressed, and came to complete this invention.

According to the present invention,
A thermosetting resin composition used for forming an insulating layer in a printed wiring board,
A benzoxazine compound represented by the following general formula (B-1) or (B-2), which contains a group having an unsaturated double bond;
A thermosetting resin containing at least one of a maleimide compound, an epoxy resin and a cyanate resin;
A thermosetting resin composition comprising an inorganic filler is provided.

Also according to the invention,
A carrier substrate;
There is provided a resin film with a carrier comprising a resin film formed on the carrier base material and formed from the thermosetting resin composition.

Also according to the invention,
There is provided a prepreg obtained by impregnating a fiber base material with the thermosetting resin composition.

Also according to the invention,
There is provided a metal-clad laminate comprising a cured product of the prepreg and a metal layer disposed on at least one surface of the cured product.

Also according to the invention,
A resin substrate provided with an insulating layer composed of a cured product of the thermosetting resin composition is provided.

Also according to the invention,
A printed wiring board comprising the metal-clad laminate or the resin substrate and a circuit layer formed on the surface of the metal-clad laminate or the resin substrate is provided.

Also according to the invention,
The printed wiring board;
There is provided a semiconductor device comprising a semiconductor element mounted on a circuit layer of the printed wiring board or built in the printed wiring board.

According to the present invention, there are provided a thermosetting resin composition capable of obtaining an insulating layer excellent in low warpage, a resin film with a carrier, a prepreg, a metal-clad laminate, a resin substrate, a printed wiring board, and a semiconductor device using the same. Provided.

FIG. 1 is a cross-sectional view showing an example of the configuration of the resin film with a carrier in the present embodiment. 2A and 2B are cross-sectional views showing an example of the configuration of the printed wiring board in the present embodiment. 3A and 3B are cross-sectional views showing an example of the configuration of the semiconductor device in the present embodiment. 4A to 4C are process cross-sectional views illustrating an example of the manufacturing process of the printed wiring board in the present embodiment. FIG. 5 is a cross-sectional view showing an example of the configuration of the printed wiring board in the present embodiment. FIG. 6 is a cross-sectional view showing an example of the configuration of the printed wiring board in the present embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

The thermosetting resin composition of the present embodiment includes a benzoxazine compound represented by the following general formula (B-1) or (B-2) containing a group having an unsaturated double bond, a maleimide compound, A thermosetting resin containing at least one of an epoxy resin and a cyanate resin and an inorganic filler are included.

(In the general formula (B-1), a independently represents an integer of 1 to 3, and p represents an integer of 1 to 4. R ₁ and R ₂ each independently represents a hydrogen atom, Represents a lower alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a monovalent to tetravalent organic group, wherein at least one of R ₁ and R ₂ represents an alkenyl group having 3 to 14 carbon atoms. (However, when p is an integer of 2 or more and 4 or less, R ₂ may be the same or different.) Z represents a monovalent to tetravalent organic group.)

(In the above general formula (B-2), each b independently represents an integer of 1 or more and 4 or less, q represents an integer of 1 or more and 4 or less. R ₃ independently represents a hydrogen atom or lower alkyl. Group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a monovalent to tetravalent organic group, and X ₁ represents a monovalent to tetravalent organic group, at least _one of R ₃ and X ₁ One is a group having an alkenyl group having 3 to 14 carbon atoms.)
Such a thermosetting resin composition is used for forming an insulating layer in a printed wiring board.

The present inventor further examined the thermosetting resin composition used for forming the insulating layer in the printed wiring board, and focused on the variety of reactions depending on the functional group of the benzoxazine compound.
As a result of examination based on such points of view, it was found that the curing characteristics of the thermosetting resin composition can be improved by using a benzoxazine compound containing a group having an unsaturated double bond as a functional group. did. In the present embodiment, the group having an unsaturated double bond is, for example, an alkenyl group having 3 to 14 carbon atoms, and an allyl group is preferable.

As a result of intensive studies based on such findings, a benzoxazine compound and a maleimide compound represented by the above general formula (B-1) or (B-2), which contain a group having an unsaturated double bond, By using together with a thermosetting resin containing at least one of an epoxy resin and a cyanate resin, the linear expansion coefficient of the obtained cured product can be lowered. For this reason, it discovered that the curvature of the printed wiring board in a manufacturing process could be suppressed, and came to complete this invention.

Although the detailed mechanism is not clear, ring-opening polymerization of a benzoxazine compound containing a group having an unsaturated double bond, catalytic action on a thermosetting resin such as a maleimide compound, or a crosslinking reaction with a thermosetting resin, etc. It is considered that the curing characteristics of the thermosetting resin composition can be enhanced by the various reaction mechanisms.

Moreover, according to this embodiment, since the curing characteristic of the thermosetting resin composition can be enhanced, the linear expansion coefficient of the obtained cured product can be lowered. Moreover, such a thermosetting resin composition has curing characteristics excellent in low-temperature curing. By using a cured product of the resin film formed from the thermosetting resin composition of the present embodiment, the curing temperature during the manufacturing process can be set low, so that the warpage of the printed wiring board can be effectively reduced. .

Moreover, according to this embodiment, the crosslinking density can be increased by various reactions in the thermosetting resin composition. Therefore, the heat resistance of the obtained cured product can be increased. That is, the structure of the cured product of the thermosetting resin composition of the present embodiment is excellent in thermal decomposition resistance.

Thus, by using the cured product of the resin film of the present embodiment for the insulating layer of the printed wiring board, the linear expansion coefficient of the insulating layer can be lowered and the curing temperature can be set to a low value. Therefore, it is possible to suppress panel warpage during a panel level process for manufacturing a large area panel size package.

In this embodiment, the insulating layer in the printed wiring board can be used as an insulating member constituting the printed wiring board such as a core layer, a build-up layer (interlayer insulating layer), a solder resist layer, and the like. The printed wiring board includes a core layer, a build-up layer (interlayer insulating layer), a printed wiring board having a solder resist layer, a printed wiring board having no core layer, a coreless board used for a panel package process (PLP), MIS (Molded Interconnect Substrate) substrate and the like.

The cured product of the resin film formed from the thermosetting resin composition of the present embodiment is used for the insulating layer. Such a cured product is, for example, a build-up layer or a solder resist layer in a printed wiring board having no core layer, an interlayer insulating layer or a solder resist layer of a coreless substrate used in PLP, an interlayer insulating layer or a solder resist layer of a MIS substrate, Etc. can also be used. As described above, the cured product of the resin film according to the present embodiment is an interlayer insulating layer or a solder resist that constitutes the printed wiring board in a large-area printed wiring board used to collectively create a plurality of semiconductor packages. It can also be suitably used for the layer.

Moreover, it is although it does not specifically limit as a utilization form of the thermosetting resin composition of this embodiment, For example, the resin film formed from the said thermosetting resin composition, The said resin film was provided on the carrier base material. A resin film with a carrier, a prepreg obtained by impregnating a fiber base material with the thermosetting resin composition, a metal-clad laminate in which a metal layer is disposed on at least one surface of a cured product of the prepreg, and the thermosetting resin composition And a printed circuit board having a circuit layer formed on the surface of the metal-clad laminate or the resin substrate.

Next, each component of the thermosetting resin composition of the present embodiment will be described.

The thermosetting resin composition of the present embodiment includes, for example, a thermosetting resin, a benzoxazine compound, and an inorganic filler.

(Thermosetting resin)
As a thermosetting resin, at least 1 type of a maleimide compound, an epoxy resin, and cyanate resin can be included, for example. These may be used alone or in combination of two or more.

(Maleimide compound)
The thermosetting resin composition of this embodiment can contain a maleimide compound.
In this embodiment, the maleimide group of the maleimide compound has a five-membered planar structure. Moreover, the double bond of the maleimide group is easy to interact between molecules and has high polarity. Therefore, a strong intermolecular interaction is exhibited with a maleimide group, a benzene ring, other compounds having a planar structure, and the like, and molecular motion can be suppressed. Therefore, when the thermosetting resin composition contains a maleimide compound, the linear expansion coefficient of the obtained insulating layer can be lowered, the glass transition temperature can be improved, and the heat resistance can be further improved.

The maleimide compound is preferably a maleimide compound having at least two maleimide groups in the molecule.
Examples of maleimide compounds having at least two maleimide groups in the molecule include 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2-bis [4- (4-maleimide). Phenoxy) phenyl] propane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide, N, N'-ethylenedimaleimide, N, N'- Hexamethylene dimaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, etc. Compound with two maleimide groups in the molecule Things, a compound having three or more maleimide groups in the molecule, such as polyphenyl methane maleimide, and the like.
One of these can be used alone, or two or more can be used in combination. Among these maleimide compounds, 4,4′-diphenylmethane bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis- (3-ethyl-) is used because of its low water absorption. 5-Methyl-4-maleimidophenyl) methane, polyphenylmethanemaleimide, and bisphenol A diphenyl ether bismaleimide are preferred.

The maleimide compound preferably includes a maleimide compound represented by the following formula (1).

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

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

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

Specific examples of the branched alkylene group include —C (CH ₃ ) ₂ — (isopropylene group), —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C Alkylmethylene groups 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.

R ₁ is independently a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrocarbon group having 1 or 2 carbon atoms, specifically a methyl group or an ethyl group. .

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

N ₁ is an integer of 0 or more and 10 or less, preferably an integer of 0 or more and 6 or less, more preferably an integer of 0 or more and 4 or less, and particularly preferably an integer of 0 or more and 3 or less. preferable. Moreover, it is more preferable that the maleimide compound includes at least a compound in which n ₁ is 1 or more in the above formula (1). Thereby, the insulating layer obtained from a thermosetting resin composition 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 an aromatic ring alone or may have a hydrocarbon group other than the aromatic ring. Y may have one aromatic ring or two or more aromatic rings, and in the case of two or more, these aromatic rings may be the same or different. The aromatic ring may be a monocyclic structure or a polycyclic structure.

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

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

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

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

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, and is preferably 0.

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

From the above, in the maleimide compound 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 hydrocarbon. 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 a thermosetting resin composition exhibits more excellent low heat shrinkability and chemical resistance.

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

Further, the maleimide compound may include a different type of maleimide compound from the maleimide compound represented by the above formula (1).
Such maleimide compounds include 1,6′-bismaleimide- (2,2,4-trimethyl) hexane, hexamethylenediamine bismaleimide, N, N′-1,2-ethylenebismaleimide, N, N ′. Aliphatic maleimide compounds such as -1,3-propylene bismaleimide and N, N′-1,4-tetramethylene bismaleimide; imide extended bismaleimide and the like. Among these, 1,6′-bismaleimide- (2,2,4-trimethyl) hexane and imide-extended bismaleimide are particularly preferable. A maleimide compound may be used independently and may use 2 or more types together.
Examples of the imide-expanded bismaleimide include a maleimide compound represented by the following formula (a1), a maleimide compound represented by the following formula (a2), a maleimide compound represented by the following formula (a3), and the like. Specific examples of the maleimide compound represented by the formula (a1) include BMI-1500 (manufactured by Designer Molecules Co., Ltd., molecular weight 1500). Specific examples of the maleimide 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. . Specific examples of the maleimide compound represented by the formula (a3) include BMI-3000 (manufactured by Designa Molecules Co., Ltd., molecular weight 3000).

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

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

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

The lower limit of the weight average molecular weight (Mw) of the maleimide compound is not particularly limited, but is preferably Mw 400 or more, particularly preferably Mw 800 or more. When Mw is equal to or more than the lower limit, it is possible to suppress the occurrence of tackiness in the insulating layer. Although the upper limit of Mw is not specifically limited, Mw4000 or less is preferable and Mw2500 or less is more preferable. When Mw is not more than the above upper limit value, handling properties are improved during the production of the insulating layer, and it becomes easy to form the insulating layer. The Mw of the maleimide compound can be measured, for example, by GPC (gel permeation chromatography, standard substance: converted to polystyrene).

Also, as the maleimide compound, a reaction product of a maleimide compound and an amine compound can be used. As the amine compound, at least one selected from an aromatic diamine compound and a monoamine compound can be used.

Examples of the aromatic diamine compound include o-dianisidine, o-tolidine, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2 ′. -Dimethyl-4,4'-diaminobiphenyl, m-phenylenediamine, p-phenylenediamine, o-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 4,4 ′-(p-phenylenediisopropylidene) dianiline, 2,2- [4- (4 -Aminophenoxy) phenyl] propane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane Bis (4- (4-aminophenoxy) phenyl) sulfone and the like.

Examples of the monoamine compound include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, m-amino. Benzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, o-aniline, m-aniline, p-aniline, o-methylaniline, m-methylaniline, p- Examples include methylaniline, o-ethylaniline, m-ethylaniline, p-ethylaniline, o-vinylaniline, m-vinylaniline, p-vinylaniline, o-allylaniline, m-allylaniline, p-allylaniline, etc. It is done.

The reaction between the maleimide compound and the amine compound can be performed in an organic solvent. The reaction temperature is, for example, 70 to 200 ° C., and the reaction time is, for example, 0.1 to 10 hours.

In the present embodiment, the content of the maleimide compound contained in the thermosetting resin composition is not particularly limited, but the total solid content of the thermosetting resin composition (that is, the component excluding the solvent) is 100% by weight. 1.0 wt% or more and 25.0 wt% or less is preferable, and 3.0 wt% or more and 20.0 wt% or less is more preferable. When the content of the maleimide compound is within the above range, the balance of low heat shrinkage and chemical resistance of the obtained insulating layer can be further improved.

(Epoxy resin)
The thermosetting resin composition of this embodiment can contain an epoxy resin.
In the present embodiment, examples of the epoxy resin 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'-cyclohexyldiene bisphenol type epoxy resin); phenol novolak type epoxy resin, cresol novolak type epoxy resin, tetraphenol group ethane type novolak type epoxy resin, condensed ring aromatic carbonization Novolac type epoxy resins such as novolak type epoxy resins having an elementary structure; 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, naphthalene Diol type epoxy resin, bifunctional to tetrafunctional naphthalene type epoxy resin, binaphthyl type epoxy resin, naphthalene type epoxy resin such as naphthalene aralkyl type epoxy resin; anthracene type epoxy resin; phenoxy type epoxy resin; dicyclopentadiene type epoxy resin; norbornene Type epoxy resin; adamantane type epoxy resin; fluorene type epoxy resin and the like.

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

Among epoxy resins, bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthalene type epoxy resin, from the viewpoint of further improving the heat resistance and insulation reliability of the obtained printed wiring board At least one or more of anthracene type epoxy resin and dicyclopentadiene type epoxy resin are preferable, and at least of aralkyl type epoxy resin, novolak type epoxy resin having condensed ring aromatic hydrocarbon structure and naphthalene type epoxy resin One type or two or more types 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. Aralkyl epoxy resins include “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 these epoxy resins, aralkyl type epoxy resins are particularly preferable. By using the aralkyl type epoxy resin, the moisture absorption solder heat resistance and flame retardancy of the cured resin film can be further improved.

The aralkyl type epoxy resin is represented by the following general formula (1), for example.

(In the general formula (1), A and B represent aromatic rings such as a benzene ring, a biphenyl structure, and a naphthalene structure. Hydrogen in the aromatic rings of A and B may be substituted. Examples of the substituent include a methyl group, an ethyl group, a propyl group, a phenyl group, etc. n represents a repeating unit, for example, an integer of 1 to 10.)

Specific examples of the aralkyl type epoxy resin include the following formulas (1a) and (1b).

(In the formula (1a), n represents an integer of 1 to 5)

(In the formula (1b), n represents an integer of 1 to 5)

As the epoxy resin other than the above, a novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure is preferable. Thereby, heat resistance and low thermal expansibility can further be improved.

The novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure is a novolak type epoxy resin having a naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, triphenylene, tetraphen, or other condensed ring aromatic hydrocarbon structure. . The novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure is excellent in low thermal expansion because a plurality of aromatic rings can be regularly arranged. Moreover, since the glass transition temperature is also high, it is excellent in heat resistance. Furthermore, since the molecular weight of the repeating structure is large, the flame retardancy is excellent as compared with the conventional novolac type epoxy resin.

The novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure is a resin obtained by epoxidizing a novolak type phenol resin synthesized from a phenol compound, an aldehyde compound, and a condensed ring aromatic hydrocarbon compound.

The phenol compound is not particularly limited, and examples thereof include phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2, Xylenols such as 6-xylenol, 3,4-xylenol, 3,5-xylenol; trimethylphenols such as 2,3,5 trimethylphenol; ethyl such as o-ethylphenol, m-ethylphenol, p-ethylphenol Phenols; alkylphenols such as isopropylphenol, butylphenol and t-butylphenol; phenylphenols such as o-phenylphenol, m-phenylphenol and p-phenylphenol; 1,5-dihydroxynaphthalene and 1,6-dihydroxynaphtha And naphthalenediols such as 2,7-dihydroxynaphthalene; polyphenols such as resorcin, catechol, hydroquinone, pyrogallol and fluoroglucin; and alkyl polyphenols such as alkylresorcin, alkylcatechol and alkylhydroquinone . Of these, phenol is preferable from the viewpoint of cost and the effect on the decomposition reaction.

Aldehyde compounds are not particularly limited, for example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, Examples include benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, dihydroxybenzaldehyde, trihydroxybenzaldehyde, 4-hydroxy-3-methoxyaldehyde paraformaldehyde and the like.

The condensed ring aromatic hydrocarbon compound is not particularly limited, but for example, naphthalene derivatives such as methoxynaphthalene and butoxynaphthalene; anthracene derivatives such as methoxyanthracene; phenanthrene derivatives such as methoxyphenanthrene; other tetracene derivatives; chrysene derivatives; pyrene derivatives; A triphenylene derivative; a tetraphen derivative and the like.

The novolak-type epoxy resin having a condensed ring aromatic hydrocarbon structure is not particularly limited. For example, methoxynaphthalene-modified orthocresol novolak epoxy resin, butoxynaphthalene-modified meta (para) cresol novolak epoxy resin, and methoxynaphthalene-modified novolak epoxy resin Etc. Among these, a novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure represented by the following general formula (V) is preferable.

(In the above general formula (V), Ar is a condensed ring aromatic hydrocarbon group, Rs may be the same or different from each other, hydrogen atom; hydrocarbon group having 1 to 10 carbon atoms; halogen An element; an aryl group such as a phenyl group or a benzyl group; and a group selected from organic groups including glycidyl ether, wherein n, p, and q are integers of 1 or more, and the values of p and q are determined for each repeating unit. May be the same or different.)
In addition, Ar in the formula (V) may have a structure represented by (Ar1) to (Ar4) in the following formula (VI).

(Rs in the above formula (VI) may be the same as or different from each other; a hydrogen atom; a hydrocarbon group having 1 to 10 carbon atoms; a halogen element; an aryl group such as a phenyl group or a benzyl group; And a group selected from organic groups including glycidyl ether.)

Further, as the epoxy resin other than the above, naphthalene type epoxy resins such as naphthol type epoxy resin, naphthalene diol type epoxy resin, bifunctional to tetrafunctional naphthalene type epoxy resin, naphthylene ether type epoxy resin and the like are preferable. Thereby, the heat resistance and low thermal expansibility of the printed wiring board to be obtained can be further improved. Here, the naphthalene type epoxy resin refers to a resin having a naphthalene ring skeleton and having two or more glycidyl groups.
In addition, since the π-π stacking effect of the naphthalene ring is higher than that of the benzene ring, the naphthalene type epoxy resin is particularly excellent in low thermal expansion and low thermal shrinkage. Further, since the polycyclic structure has a high rigidity effect and the glass transition temperature is particularly high, the change in heat shrinkage before and after reflow is small. As the naphthol type epoxy resin, for example, the following general formula (VII-1), as the naphthalene diol type epoxy resin, the following formula (VII-2), as the bifunctional or tetrafunctional naphthalene type epoxy resin, the following formula (VII-3) Examples of (VII-4) (VII-5) and naphthylene ether type epoxy resin can be represented by the following general formula (VII-6).

(N represents an average number of 1 to 6, and R represents a glycidyl group or a hydrocarbon group having 1 to 10 carbon atoms.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aralkyl group, a naphthalene group, or a glycidyl ether group-containing naphthalene group. , O and m are each an integer of 0 to 2, and either o or m is 1 or more.)

The lower limit of the weight average molecular weight (Mw) of the epoxy resin is not particularly limited, but is preferably 300 or more, more preferably 800 or more. It can suppress that tackiness arises in the hardened | cured material of a resin film as Mw is more than the said lower limit. The upper limit of Mw is not particularly limited, but is preferably Mw 20,000 or less, and more preferably Mw 15,000 or less. When Mw is not more than the above upper limit value, the handling property is improved and it becomes easy to form a resin film. The Mw of the epoxy resin can be measured by GPC, for example.

The lower limit of the content of the epoxy resin is preferably 3% by weight or more, more preferably 4% by weight or more, more preferably 5% by weight with respect to 100% by weight of the entire thermosetting resin composition (total solid content excluding the solvent). The above is more preferable. When the content of the epoxy resin is not less than the above lower limit value, handling properties are improved, and it becomes easy to form a resin film. On the other hand, the upper limit of the content of the epoxy resin is not particularly limited with respect to the entire thermosetting resin composition (total solid content excluding the solvent), but is preferably 40% by weight or less, for example, 30% by weight or less. More preferred is 20% by weight or less. When the content of the epoxy resin is not more than the above upper limit, the strength and flame retardancy of the obtained printed wiring board are improved, the linear expansion coefficient of the printed wiring board is lowered, and the warp reduction effect is improved. There is a case.
In addition, the total solid content of a thermosetting resin composition refers to the whole component except the solvent contained in a thermosetting resin composition. The same applies hereinafter.

(Cyanate resin)
The thermosetting resin composition of the present embodiment can contain a cyanate resin.
In the present embodiment, the cyanate resin is a resin having a cyanate group (—O—CN) in the molecule, and a resin having two or more cyanate groups in the molecule can be used. Such a cyanate resin is not particularly limited. For example, it can be obtained by reacting a halogenated cyanide compound with phenols or naphthols, and prepolymerizing by a method such as heating as necessary. Moreover, the commercial item prepared in this way can also be used.
By using cyanate resin, the linear expansion coefficient of the cured resin film can be reduced. Furthermore, the electrical properties (low dielectric constant, low dielectric loss tangent), mechanical strength, etc. of the cured resin film can be enhanced.

Examples of the cyanate resin include novolak type cyanate resin; bisphenol type cyanate resin, bisphenol E type cyanate resin, bisphenol type cyanate resin such as tetramethylbisphenol F type cyanate resin; reaction of naphthol aralkyl type phenol resin and cyanogen halide. Naphthol aralkyl type cyanate resin obtained by the following: dicyclopentadiene type cyanate resin; biphenylalkyl type cyanate resin. Among these, novolak type cyanate resins and naphthol aralkyl type cyanate resins are preferable, and novolak type cyanate resins are more preferable. By using the novolac-type cyanate resin, the crosslink density of the cured product of the resin film is increased, and the heat resistance is improved.

The reason for this is that the novolac-type cyanate resin forms a triazine ring after the curing reaction. Furthermore, it is considered that novolak-type cyanate resin has a high benzene ring ratio due to its structure and is easily carbonized. Moreover, the cured product of the resin film containing the novolak type cyanate resin has excellent rigidity. Therefore, the heat resistance of the cured resin film can be further improved.

As the novolac-type cyanate resin, for example, a resin represented by the following general formula (I) can be used.

The average repeating unit n of the novolak cyanate resin represented by the general formula (I) is an arbitrary integer. The average repeating unit n is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. When the average repeating unit n is not less than the above lower limit, the heat resistance of the novolak cyanate resin is improved, and it is possible to suppress the demerization and volatilization of the low mer during heating. The average repeating unit n is not particularly limited, but is preferably 10 or less, more preferably 7 or less. It can suppress that melt viscosity becomes it high that n is below the said upper limit, and can improve the moldability of a resin film.

As the cyanate resin, a naphthol aralkyl type cyanate resin represented by the following general formula (II) is also preferably used. The naphthol aralkyl type cyanate resin represented by the following general formula (II) includes, for example, naphthols such as α-naphthol or β-naphthol, p-xylylene glycol, α, α'-dimethoxy-p-xylene, 1,4 A resin obtained by condensing a naphthol aralkyl type phenol resin obtained by reaction with di (2-hydroxy-2-propyl) benzene or the like and cyanogen halide. The repeating unit n in the general formula (II) is preferably an integer of 10 or less. When the repeating unit n is 10 or less, a more uniform resin film can be obtained. In addition, intramolecular polymerization hardly occurs at the time of synthesis, the liquid separation property at the time of washing with water tends to be improved, and the decrease in yield tends to be prevented.

(In the formula, each R independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more and 10 or less.)

In addition, one kind of cyanate resin may be used alone, two or more kinds may be used in combination, and one kind or two or more kinds and a prepolymer thereof may be used in combination.

The lower limit of the content of the cyanate resin is, for example, preferably 1% by weight or more, more preferably 2% by weight or more, and further more preferably 3% by weight or more with respect to 100% by weight of the total solid content of the thermosetting resin composition. preferable. It is possible to achieve low linear expansion and high elastic modulus of the cured resin film. On the other hand, the upper limit of the content of the cyanate resin is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, but is preferably 30% by weight or less, and more preferably 25% by weight or less. 20% by weight or less is more preferable. Heat resistance and moisture resistance can be improved. Further, when the content of the cyanate resin is within the above range, the storage elastic modulus E ′ of the cured product of the resin film can be further improved.

(Benzoxazine compound)
The thermosetting resin composition of this embodiment contains a benzoxazine compound.
As described above, in the present embodiment, the benzoxazine compound contains a group having an unsaturated double bond. The group having an unsaturated double bond is preferably an alkenyl group having 3 to 14 carbon atoms, more preferably an allyl group.

The benzoxazine compound used in the present embodiment is represented by the following general formula (B-1) or general formula (B-2). These may be used alone or in combination of two or more.

In the general formula (B-1), when p = 1, Z represents an alkyl group or a thiol, and when p = 2, Z is a direct bond, an alkylene group, an oxygen atom, a sulfur atom, A sulfinyl group or a sulfonyl group is represented. When p = 3 or 4, Z may represent an alkylene group. In the general formula (B-1), p may be 2. Further, a may be 1.

(In the above general formula (B-2), each b independently represents an integer of 1 or more and 4 or less, q represents an integer of 1 or more and 4 or less. R ₃ independently represents a hydrogen atom or lower alkyl. Group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a monovalent to tetravalent organic group, and X ₁ represents a monovalent to tetravalent organic group, at least _one of R ₃ and X ₁ One is an alkenyl group having 3 to 14 carbon atoms.)
In the general formula (B-2), q may be 2. Further, b may be 1.

In the present embodiment, the monovalent to tetravalent organic group is not particularly limited. In addition to the direct bond, the alkyl group, the alkylene group, the oxygen atom, the thiol, the sulfur atom, the sulfoxide, and the sulfone, for example, the following chemical formula Any of these may be used. Note that biphenyl, diphenylmethane, diphenylisopropane, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, and diphenyl ketone may be used as the monovalent to tetravalent organic group in the general formula (B-2). These may be used alone or in combination of two or more.

R _{1 in the} above chemical formula is the same as R ₁ defined in the general formula (B-1), specifically, a hydrogen atom, a lower alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Represents.

In this embodiment, the benzoxazine compound represented by the general formula (B-1) may be a compound having a structure represented by the following general formula (B-3).

(In the above general formula (B-3), Z represents a direct bond, an alkylene group having 1 to 10 carbon atoms, C═O, O, S, S═O or O═S═O. R ₁ and / R ₂ is a group having an alkenyl group having 3 to 14 carbon atoms, wherein R ₁ and R ₂ in the general formula (B-3) are R defined in the general formula (B-1). ₁ and R ₂ are the same.)

An example of the benzoxazine compound represented by the general formula (B-3) is represented by the following general formula. In the following general formula, R ₁ and R ₂ are the same as R ₁ and R ₂ defined in the general formula (B-1).

In the above general formula, R ₁ may be an alkenyl group having 3 to 14 carbon atoms, but is preferably an allyl group. At this time, R ₂ may be a hydrogen atom.

In this embodiment, the benzoxazine compound represented by the general formula (B-2) may have a structure represented by the following general formula (B-4).

(In the general formula (B-4), c each independently represents an integer of 1 to 4, X ₂ is a direct bond, an alkylene group having 1 to 10 carbon atoms, C═O, O (oxygen atom). , S (sulfur atom), S═O (sulfinyl group) or O═S═O (sulfonyl group), R is a group having an alkenyl group having 3 to 14 carbon atoms.

In the general formula (B-4), c may be 1, for example. R may be an allyl group. X ₂ may be an alkylene group having 1 to 10 carbon atoms.

An example of the benzoxazine compound represented by the general formula (B-4) is represented by the following general formula.

The lower limit of the content of the benzoxazine compound is not particularly limited. For example, when the total solid content (that is, the component excluding the solvent) of the thermosetting resin composition is 100% by weight, the lower limit is 1% by weight or more. It is preferably 2% by weight or more, more preferably 3% by weight or more. Thereby, the low heat-shrinkage property and chemical resistance of the hardened | cured material and resin substrate which are obtained can be improved further. Further, the upper limit of the content of the benzoxazine compound is not particularly limited. For example, when the total solid content of the thermosetting resin composition is 100% by weight, it is preferably 25% by weight or less, and 23% by weight or less. Is more preferable, and 20% by weight or less is more preferable. Thereby, the reaction efficiency with another compound can be improved.

The content of the maleimide compound contained in the thermosetting resin composition of the present embodiment is preferably 35% by weight or more and 80% by weight or less with respect to 100% by weight of the total of the maleimide compound and the benzoxazine compound. Thereby, the heat resistance of the hardened | cured material and resin substrate which are obtained, low heat shrinkability, and chemical resistance can be improved further.
Further, in the thermosetting resin composition of the present embodiment, epoxy equivalent / phenol equivalent at the time of ring opening is not particularly limited, but is preferably 0.05 or more and 20 or less, and more preferably 0.1 or more and 15 or less. 0.5 to 10 is more preferable, and 1 to 5 is most preferable.
In the thermosetting resin composition of the present embodiment, the molar ratio of cyanate resin: benzoxazine compound is not particularly limited, but for example, 99.9: 0.1 to 0.1: 99.9 is preferable. 90:10 to 0.5: 99.5 is more preferable, 65:35 to 1:99 is more preferable, and 50:50 to 5:95 is most preferable.

(Inorganic filler)
The thermosetting resin composition of this embodiment can contain an inorganic filler.
Examples of the inorganic filler 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, magnesium carbonate and hydro Carbonates such as talcite; 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, boric acid Examples thereof include borates such as aluminum, calcium borate, and sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride, and carbon nitride; titanates such as strontium titanate and barium titanate.
Among these, talc, alumina, glass, silica, mica, aluminum hydroxide, and magnesium hydroxide are preferable, and silica is particularly preferable. As the inorganic filler, one of these may be used alone, or two or more may be used in combination.

Although the lower limit of the average particle diameter of the inorganic filler is not particularly limited, for example, 0.01 μm or more is preferable, and 0.05 μm or more is more preferable. Thereby, it can suppress that the viscosity of the varnish of the said thermosetting resin becomes high, and can improve the workability | operativity at the time of insulation layer preparation. Moreover, the upper limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 5.0 μm or less, more preferably 2.0 μm or less, and further preferably 1.0 μm or less. Thereby, phenomena, such as sedimentation of the inorganic filler in the varnish of the said thermosetting resin, can be suppressed, and a more uniform resin film can be obtained. Moreover, when the circuit dimension L / S of the printed wiring board is less than 20 μm / 20 μm, it is possible to suppress the influence on the insulation between the wirings.
In the present embodiment, the average particle size of the inorganic filler is determined by measuring the particle size distribution of the particles on a volume basis using, for example, a laser diffraction particle size distribution measuring apparatus (LA-500, manufactured by HORIBA), and the median diameter (D50 ) May be the average particle size.

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

The inorganic filler preferably contains silica particles. The average particle diameter of the silica particles is not particularly limited, but is preferably 5.0 μm or less, more preferably 0.1 μm or more and 4.0 μm or less, and further preferably 0.2 μm or more and 2.0 μm or less. Thereby, the filling property of the inorganic filler can be further improved.

The lower limit of the content of the inorganic filler is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, for example, preferably 50% by weight or more, more preferably 55% by weight or more, 60% by weight or more is more preferable. Thereby, the cured product of the resin film can have particularly low thermal expansion and low water absorption. Further, the warpage of the semiconductor package can be suppressed. On the other hand, the upper limit of the content of the inorganic filler is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, but is preferably 90% by weight or less, for example, 85% by weight or less. More preferred is 80% by weight or less. Thereby, the workability of the cured product of the resin film can be improved.

(Curing agent)
The thermosetting resin composition of the present embodiment can contain a curing agent.
The curing agent is not particularly limited. For example, tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2- Ethyl-4-methylimidazole (EMI24), 2-phenyl-4-methylimidazole (2P4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-methyl-5-hydroxyimidazole (2P4MHZ), 1-benzyl- imidazole compounds such as 2-phenylimidazole (1B2PZ); catalyst type curing agents include Lewis acids such as BF ₃ complex.
Also, for example, aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), m-phenylenediamine, p-phenylenediamine, o-xylenediamine, 4,4′- Diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 4,4'- (P-phenylenediisopropylidene) dianiline, 2,2- [4- (4-aminophenoxy) phenyl] propane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3 , 3'-diethyl-5,5'-dimethyldiphenylmethane, 3 In addition to aromatic polyamines such as 3'-diethyl-4,4'-diaminodiphenylmethane, polyamine compounds including dicyandiamide (DICY), organic acid dihydrazide, etc .; hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA) Acid anhydrides including aromatic acid anhydrides such as alicyclic acid anhydrides such as, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); polysulfide, thioester, Polymercaptan compounds such as thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; polyaddition type curing agents such as organic acids such as carboxylic acid-containing polyester resins; 2,2′-methylenebis (4-ethyl-6- t ert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3- Methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydroquinone, 1,3,5-tris (3,5-di-tert) Phenolic compounds such as -butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) trione can also be used.
Furthermore, as the second curing agent, for example, a phenol resin-based curing agent such as a novolak type phenol resin or a resol type phenol resin; a urea resin such as a methylol group-containing urea resin; a melamine resin such as a methylol group-containing melamine resin; A condensation type curing agent may also be used. These may be used alone or in combination of two or more.

The phenol resin-based curing agent is a monomer, oligomer, or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, a phenol novolak resin, a cresol novolak resin, Novolak type phenolic resin such as naphthol novolak resin; polyfunctional phenolic resin such as triphenolmethane type phenolic resin; modified phenolic resin such as terpene modified phenolic resin and dicyclopentadiene modified phenolic resin; phenylene skeleton and / or biphenylene skeleton Aralkyl resins such as phenol aralkyl resins, naphthol aralkyl resins having a phenylene and / or biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F Etc. The. These may be used alone or in combination of two or more. Among these, from the viewpoint of curability, a phenol resin-based curing agent having a hydroxyl group equivalent of 90 g / eq or more and 250 g / eq or less may be used.
The weight average molecular weight of the phenol resin is not particularly limited, but is preferably 4 × 10 ² to 1.8 × 10 ^{3 and} more preferably 5 × 10 ² to 1.5 × 10 ³ . By making the weight average molecular weight equal to or higher than the above lower limit value, problems such as tackiness occur in the prepreg, and by making the above upper limit value or less, the impregnation property to the fiber base material is improved at the time of prepreg production, A more uniform product can be obtained.

The lower limit of the content of the curing agent is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, but is preferably 0.01% by weight or more, for example, 0.05% by weight or more. More preferred is 0.2% by weight or more. By setting the content of the curing agent to the above lower limit value or more, the effect of promoting curing can be sufficiently exhibited. On the other hand, the upper limit of the content of the curing agent is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, but is preferably 15% by weight or less, and more preferably 10% by weight or less. 8% by weight or less is more preferable. The preservability of a prepreg can be improved more as content of a hardening | curing agent is below the said upper limit.

(Curing accelerator)
The thermosetting resin composition of this embodiment may contain a hardening accelerator, for example. Thereby, the sclerosis | hardenability of a thermosetting resin composition can be improved. As a hardening accelerator, the compound which accelerates | stimulates hardening reaction of a thermosetting resin can be used, The kind is not specifically limited. In this embodiment, as a hardening accelerator, for example, zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, zinc octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III) Organic metal salts such as triethylamine, tributylamine, tertiary amines such as diazabicyclo [2,2,2] octane, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, Imidazoles such as 2-phenyl-4-ethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxyimidazole , Phenol, bisphe Lumpur A, phenolic compounds nonylphenol, acetic, benzoic acid, salicylic, organic acids such as p-toluenesulfonic acid, and one or more selected from an onium salt compound. Among these, it is more preferable to include an onium salt compound from the viewpoint of more effectively improving curability.

Although the onium salt compound used as a curing accelerator is not particularly limited, for example, a compound represented by the following general formula (2) can be used.

(In the general formula (2), P is a phosphorus atom, R ³ , R ⁴ , R ⁵ and R ⁶ are each an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted group. An aliphatic group, which may be the same or different from each other, A ⁻ is an n (n ≧ 1) -valent proton donor anion having at least one proton that can be released outside the molecule in the molecule. Or a complex anion thereof)

The lower limit of the content of the curing accelerator is, for example, preferably 0.01% by weight or more, more preferably 0.1% by weight or more with respect to 100% by weight of the total solid content of the thermosetting resin composition. . By making content of a hardening accelerator more than the said lower limit, sclerosis | hardenability of a thermosetting resin composition can be improved more effectively. On the other hand, the upper limit value of the content of the curing accelerator is, for example, preferably 5% by weight or less and more preferably 1% by weight or less with respect to 100% by weight of the total solid content of the thermosetting resin composition. By making content of a hardening accelerator into the said upper limit or less, the preservability of a thermosetting resin composition can be improved.

(Coupling agent)
The thermosetting resin composition of this embodiment may contain a coupling agent. The coupling agent may be added directly when preparing the thermosetting resin composition, or may be added in advance to the inorganic filler. Use of a coupling agent can improve the wettability of the interface between the inorganic filler and each resin. Therefore, it is preferable to use a coupling agent, and the heat resistance of the cured resin film can be improved. Moreover, adhesiveness with copper foil can be improved by using a coupling agent. Furthermore, since the moisture absorption resistance can be improved, the adhesion with the copper foil can be maintained even after the humidity environment.

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. In this embodiment, the coupling agent may contain a silane coupling agent.
Thereby, the wettability of the interface of an inorganic filler and each resin can be made high, and the heat resistance of the hardened | cured material of a resin film can be improved more.

The silane coupling agent is not particularly limited, and examples thereof include epoxy silane, amino silane, alkyl silane, ureido silane, mercapto silane, and vinyl silane.

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

The content of the coupling agent can be appropriately adjusted with respect to the specific surface area of the inorganic filler. The lower limit of the content of such a coupling agent is, for example, preferably 0.01% by weight or more, more preferably 0.05% by weight or more with respect to 100% by weight of the total solid content of the thermosetting resin composition. preferable. When the content of the coupling agent is not less than the above lower limit, the inorganic filler can be sufficiently covered, and the heat resistance of the cured product of the resin film can be improved. On the other hand, the upper limit of the content of the coupling agent is, for example, preferably 2% by weight or less, and more preferably 1% by weight or less with respect to 100% by weight of the total solid content of the thermosetting resin composition. When the content of the coupling agent is not more than the above upper limit value, it is possible to suppress the influence on the reaction, and it is possible to suppress a decrease in the bending strength or the like of the cured product of the resin film.

(Additive)
The thermosetting resin composition of the present embodiment is a dye such as green, red, blue, yellow, and black, a pigment such as a black pigment, and a dye within a range that does not impair the object of the present invention. One or more colorants, low-stress agents, antifoaming agents, leveling agents, UV absorbers, foaming agents, antioxidants, flame retardants, ion scavengers, and other components (thermosetting resins, curing agents, inorganic fillers) Additives other than materials, curing accelerators, and coupling agents) may be included. These may be used alone or in combination of two or more.

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

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

In this embodiment, the varnish-like thermosetting resin composition can contain a solvent.
Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol, anisole, And organic solvents such as N-methylpyrrolidone. These may be used alone or in combination of two or more.

When the thermosetting resin composition is varnished, the solid content of the thermosetting resin composition is preferably, for example, 30% by weight to 80% by weight, and more preferably 40% by weight to 70% by weight. . Thereby, the thermosetting resin composition excellent in workability | operativity and film formability is obtained.

The varnish-like thermosetting resin composition comprises the above-described components, for example, an ultrasonic dispersion method, a high-pressure collision dispersion method, a high-speed rotation dispersion method, a bead mill method, a high-speed shear dispersion method, and a rotation and revolution dispersion method. It can prepare by melt | dissolving in a solvent, mixing, and stirring using various mixers of these.

Next, the resin film of this embodiment will be described.

The resin film of the present embodiment can be obtained by forming a film of the thermosetting resin composition having a varnish shape. For example, the resin film of this embodiment can be obtained by removing the solvent from the coating film obtained by coating a varnish-like thermosetting resin composition. In such a resin film, the solvent content can be 5% by weight or less based on the entire resin film. In the present embodiment, for example, a step of removing the solvent may be performed under conditions of 100 ° C. to 150 ° C. and 1 minute to 5 minutes. Thereby, it is possible to sufficiently remove the solvent while suppressing the curing of the resin film containing the thermosetting resin.

(Resin film with carrier)
Next, the resin film with a carrier of this embodiment will be described.
FIG. 1 is a cross-sectional view showing an example of the configuration of the resin film with carrier 100 in the present embodiment.
As shown in FIG. 1, the resin film with a carrier 100 of the present embodiment includes a carrier base material 12 and a resin film 10 formed on the carrier base material 12 and formed from the thermosetting resin composition. Can be provided. Thereby, the handleability of the resin film 10 can be improved.

The resin film with carrier 100 may be a roll shape that can be wound or a single wafer shape such as a rectangular shape.

In the present embodiment, for example, a polymer film or a metal foil can be used as the carrier substrate 12. The polymer film is not particularly limited. For example, polyolefin such as polyethylene and polypropylene, polyester such as polyethylene terephthalate and polybutylene terephthalate, release paper such as polycarbonate and silicone sheet, heat resistance such as fluorine resin and polyimide resin. A thermoplastic resin sheet having The metal foil is not particularly limited. For example, copper or copper alloy, aluminum or aluminum alloy, iron or iron alloy, silver or silver alloy, gold or gold alloy, zinc or zinc alloy, nickel Alternatively, a nickel-based alloy, tin, a tin-based alloy, or the like can be given. Among these, a sheet made of polyethylene terephthalate is most preferable because it is inexpensive and easy to adjust the peel strength. By using a sheet made of such a material as the carrier substrate 12, it becomes easy to peel the resin film 10 from the carrier substrate 12 with an appropriate strength.

The lower limit of the thickness of the resin film 10 is not particularly limited, but is preferably 1 μm or more, more preferably 3 μm or more, and further preferably 5 μm or more. Thereby, the mechanical strength of the resin film 10 can be increased. On the other hand, the upper limit value of the thickness of the resin film 10 is not particularly limited, but is preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less. Thereby, the semiconductor device can be thinned.

The thickness of the carrier substrate 12 is not particularly limited, but is preferably 10 to 100 μm, and more preferably 10 to 70 μm. Thereby, the handleability at the time of manufacturing the resin film 100 with a carrier becomes more favorable.

The resin film with carrier 100 of the present embodiment may be a single layer or a multilayer, and may include one or more types of resin films 10. When the resin sheet is multi-layered, the resin sheets may be composed of the same kind or different kinds. The resin film with carrier 100 may have a protective film on the outermost layer side on the resin film 10.

In the present embodiment, the method for forming the resin film with carrier 100 is not particularly limited. As such a method, for example, a coating film is formed by applying a varnish-like thermosetting resin composition on the carrier substrate 12 using various coater apparatuses, and then the coating film is appropriately dried. Thus, a method for removing the solvent can be used.

(Resin substrate)
The resin substrate of this embodiment can include an insulating layer composed of a cured product of the thermosetting resin composition. Such a resin substrate can be configured not to contain glass fibers and can be used for a printed wiring board.

(Prepreg)
The prepreg of the present embodiment is formed by impregnating a fiber base material with the thermosetting resin composition. For example, the prepreg can be used as a sheet-like material obtained by impregnating a thermosetting resin composition into a fiber substrate and then semi-curing the thermosetting resin composition. The sheet-like material having such a structure is excellent in various properties such as dielectric properties, mechanical and electrical connection reliability under high temperature and high humidity, and is suitable for manufacturing an insulating layer of a printed wiring board.

The method for impregnating the fiber base material with the thermosetting resin composition is not particularly limited. As such a method, for example, a method in which a thermosetting resin composition is dissolved in a solvent to prepare a resin varnish, a fiber base material is immersed in the resin varnish, and a method in which the resin varnish is applied to the fiber base material with various coaters Examples thereof include a method of spraying the resin varnish onto the fiber substrate by spraying, a method of laminating both surfaces of the fiber substrate with the resin film formed from the thermosetting resin composition, and the like.

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

(Metal-clad laminate)
In the present embodiment, the metal-clad laminate has a metal layer disposed on at least one surface of the cured product of the prepreg.
Moreover, the metal-clad laminated board manufacturing method using a prepreg is as follows, for example.
Two or more prepregs or a laminate of two or more prepregs stacked on top and bottom surfaces or one side of the laminate, metal foils are stacked and bonded under high vacuum conditions using a laminator or becquerel device, or as they are Stack metal foil on both sides or one side. Further, when two or more prepregs are laminated, the metal foil is overlaid on the outermost upper and lower surfaces or one surface of the laminated prepregs. Next, a metal-clad laminate can be obtained by heat-pressing a laminate in which a prepreg and a metal foil are stacked. Here, it is preferable to continue the pressurization until the end of cooling at the time of heat-pressure molding.

As the metal constituting the metal foil, for example, copper, copper alloy, aluminum, aluminum alloy, silver, silver alloy, gold, gold alloy, zinc, zinc alloy, nickel, nickel alloy, tin, Examples thereof include tin-based alloys, iron, iron-based alloys, Kovar (trade name), 42 alloys, Fe-Ni alloys such as Invar, Super Invar, 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, a metal foil with a carrier or the like can also be used.
The thickness of the metal foil is preferably from 0.5 μm to 20 μm, and more preferably from 1.5 μm to 18 μm.

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

Although the thickness of a fiber base material is not specifically limited, 5 micrometers or more and 150 micrometers or less are preferable, 10 micrometers or more and 100 micrometers or less are more preferable, and 12 micrometers or more and 90 micrometers or less are more preferable. 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 thermosetting resin composition 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, the handling property is improved, so that the prepreg can be easily manufactured and the warpage of the resin substrate can be suppressed.

As said glass fiber base material, the glass formed with 1 type, or 2 or more types of glass chosen from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass, and quartz glass, for example A fiber base material is preferably used.

According to the present embodiment, by employing such a resin film or a prepreg using the resin film, it is possible to configure an insulating layer in a printed wiring board with a reduced linear expansion coefficient in the planar direction.

The characteristics of the resin film of this embodiment will be described.

As described above, the resin film of the present embodiment is a resin film formed from the thermosetting resin composition.
The upper limit value of the average linear expansion coefficient in the plane direction (XY direction) calculated in the range of 30 ° C. to 240 ° C. of the cured resin film according to the present embodiment is, for example, preferably 40 ppm / ° C. or less, and 30 ppm / ° C. The following is more preferable, and 20 ppm / ° C. or less is further preferable. Thereby, the curvature of the printed wiring board during a manufacturing process can be reduced. Further, the warpage of the obtained semiconductor package can be reduced. Further, since the stress accumulated in the obtained semiconductor package can be reduced, the connection reliability is excellent. On the other hand, the lower limit value of the average linear expansion coefficient is not particularly limited, but may be, for example, 1 ppm / ° C. or higher.

Further, the upper limit value of the average linear expansion coefficient (α1) in the plane direction (XY direction) of the cured product of the resin film of the present embodiment calculated in the range of 30 ° C. to 150 ° C. is preferably, for example, 30 ppm / ° C. or less. 25 ppm / ° C. or less is more preferable, and 15 ppm / ° C. or less is more preferable. Thereby, the curvature of the printed wiring board during a manufacturing process can be reduced. Further, the warpage of the obtained semiconductor package can be reduced. On the other hand, the lower limit value of the average linear expansion coefficient (α1) is not particularly limited, but may be, for example, 1 ppm / ° C. or more.

Further, the upper limit value of the average linear expansion coefficient (α2) in the plane direction (XY direction) calculated in the range of 150 ° C. to 240 ° C. of the cured product of the resin film of the present embodiment is preferably 40 ppm / ° C. or less, for example. 35 ppm / ° C. or less is more preferable, and 30 ppm / ° C. or less is more preferable. Thereby, the curvature of the printed wiring board and the curvature of a semiconductor package at the time of high temperature thermal history can be reduced. In addition, it is possible to reduce warping during mounting in which the obtained semiconductor package is heated by reflow or the like and the upper and lower PKGs or wiring boards are connected by conductor posts such as solder balls. On the other hand, the lower limit value of the average linear expansion coefficient (α2) is not particularly limited, but may be, for example, 1 ppm / ° C. or more.

Thus, by using the cured product of the resin film of the present embodiment, it is possible to suppress warpage at room temperature (for example, 25 ° C.) and to suppress warpage even during a high temperature thermal history. Thereby, for example, during the manufacturing process, it is possible to suppress warping of a printed wiring board having a large area, and it is possible to sufficiently improve warpage of the semiconductor package and connection reliability during a thermal history.

Further, the average linear expansion coefficient calculated in the range of 30 ° C. to 150 ° C. of the cured product of the thermosetting resin composition is α1, and the cured product of the thermosetting resin composition is in the range of 150 ° C. to 240 ° C. The average coefficient of linear expansion calculated in step α is α2.
At this time, the lower limit of the average linear expansion coefficient ratio (α2 / α1) is, for example, preferably 0.7 or more, more preferably 0.8 or more, and further preferably 0.9 or more. Thereby, the balance of the linear expansion coefficient at the time of room temperature and a heat history can be raised, On the other hand, although the upper limit of the said average linear expansion coefficient ratio ((alpha) 2 / (alpha) 1) is not specifically limited, For example, 3.0 or less Is preferable, 2.8 or less is more preferable, and 2.5 or less is more preferable. Thereby, the curvature of a semiconductor package at the time of a heat history and connection reliability can fully be improved. In addition, the thermal characteristics of the semiconductor package can be improved.

In the present embodiment, the lower limit value of the glass transition temperature of the cured resin film (cured product of the thermosetting resin composition) is not particularly limited, but is preferably 140 ° C. or higher, more preferably 200 ° C. or higher, 230 degreeC or more is especially preferable. Thereby, the cured | curing material of the resin film excellent in heat resistance is obtained. Moreover, the upper limit value of the glass transition temperature of the cured resin film is not particularly limited, but may be, for example, 400 ° C. or lower.
The glass transition temperature can be measured using a dynamic viscoelasticity analyzer (DMA). The glass transition temperature corresponds to the peak value of the loss tangent tan δ existing in a region of 150 ° C. or higher in a curve obtained by dynamic viscoelasticity measurement under conditions of a temperature rising rate of 5 ° C./min and a frequency of 1 Hz. Temperature.

In this embodiment, the glass transition temperature is 180 ° C. For a cured product of the resin film obtained by heat treatment at 2 hours, for example, using a dynamic viscoelasticity measuring device, the frequency is 1 Hz, and the heating rate is 5 ° C./min. It can be calculated from the measurement result obtained by performing the dynamic viscoelasticity test under the conditions. Although it does not specifically limit as a dynamic viscoelasticity measuring apparatus, For example, a DMA apparatus (TA instrument company make, Q800) can be used.

In this embodiment, for example, the average linear expansion coefficient and the glass transition temperature of the thermosetting resin composition are desired by appropriately selecting the type and blending ratio of the components constituting the thermosetting resin composition, respectively. Can be within the range. For example, use of a benzoxazine compound having an allyl group as a functional group, use of a maleimide compound as a thermosetting resin, and the like are cited as factors for bringing the average linear expansion coefficient and glass transition temperature into a desired numerical range. Be

In the present embodiment, the lower limit value of the peel strength of the cured resin film (cured product of the thermosetting resin composition) with respect to the copper foil is not particularly limited. For example, 0.5 kN / m or more is preferable. 0.6 kN / m or more is more preferable, and 0.7 kN / m or more is more preferable. Thereby, the copper adhesiveness of the hardened | cured material of a resin film can be improved, and the SAP characteristic of the insulating layer obtained can be improved. The upper limit of the peel strength is not particularly limited, but may be, for example, 3 kN / m or less.

In the present embodiment, as a method for measuring the peel strength with respect to the copper foil, for example, a metal-clad laminate is prepared, and the peel between the cured prepreg and the metal foil is measured according to JIS C-6481: 1996. You may use the method of measuring intensity | strength after a 100-hour process on HAST conditions (temperature 130 degreeC, humidity 85%).

(Printed circuit board)
The printed wiring board of this embodiment includes an insulating layer composed of a cured product of the above resin film (cured product of a thermosetting resin composition).
In the present embodiment, the cured product of the resin film is, for example, a core layer, a buildup layer, a solder resist layer of a normal printed wiring board, a buildup layer, a solder resist layer, or a PLP in a printed wiring board having no core layer. It can be used for an interlayer insulating layer and a solder resist layer of a coreless substrate used, an interlayer insulating layer and a solder resist layer of a MIS substrate, and the like. Such an insulating layer is preferably used for an interlayer insulating layer and a solder resist layer constituting the printed wiring board in a large-area printed wiring board used to collectively create a plurality of semiconductor packages. it can.

Next, an example of the printed wiring board 300 according to the present embodiment will be described with reference to FIGS.
The printed wiring board 300 of this embodiment includes an insulating layer made of a cured product of the resin film 10 described above. As shown in FIG. 2A, the printed wiring board 300 may have a structure including an insulating layer 301 (core layer) and an insulating layer 401 (solder resist layer). Further, as shown in FIG. 2B, the printed wiring board 300 has a structure including an insulating layer 301 (core layer), an insulating layer 305 (build-up layer), and an insulating layer 401 (solder resist layer). It may be. Each of these core layer, build-up layer, and solder resist layer can be composed of, for example, a cured product of the resin film of the present embodiment. This core layer may be composed of a cured body obtained by curing a prepreg formed by impregnating a fiber base material with the thermosetting resin composition of the present embodiment.

The cured product formed from the resin film of the present embodiment may not include a fiber substrate such as a glass cloth or a paper substrate. Thereby, it can be set as the structure especially suitable in order to form a buildup layer (interlayer insulation layer) and a soldering resist layer.

Also, 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 printed wiring board in which two or more build-up layers (for example, the insulating layer 305) are stacked on the insulating layer 301 as a core layer by a plated through hole method, a build-up method, or the like. .

In the present embodiment, the via hole 307 may be a hole for electrically connecting layers, and may be either a through hole or a non-through hole. The via hole 307 may be formed by embedding a metal. The buried metal may have a structure covered with an electroless metal plating film 308.

In the present embodiment, the metal layer 303 may be, for example, a circuit pattern or an electrode pad. The metal layer 303 may have, for example, a metal laminated structure of the metal foil 105 and the electrolytic metal plating layer 309.
The metal layer 303 is, for example, on the surface of an insulating layer (for example, the insulating layer 301 or the insulating layer 305) formed from the metal foil 105 that has been subjected to chemical treatment or plasma treatment or a cured product of the resin film of the present embodiment. It is formed by the SAP (semi-additive process) method. For example, after the electroless metal plating film 308 is applied on the metal foil 105 or the insulating

layers

301 and 305, the non-circuit forming portion is protected by a plating resist, and the electrolytic metal plating layer 309 is applied by electrolytic plating. The metal layer 303 is formed by patterning the electrolytic metal plating film 309 by removal and flash etching.

Further, the printed wiring board 300 of the present embodiment can be a resin board that does not contain glass fiber. For example, the insulating layer 301 that is the core layer may be configured not to contain glass fibers. Even in a semiconductor package using such a resin substrate, the linear expansion coefficient of the cured product of the resin film can be reduced, so that package warpage can be sufficiently suppressed.

(Semiconductor package)
Next, the semiconductor device 400 of this embodiment will be described. FIGS. 3A and 3B are cross-sectional views illustrating an example of the configuration of the semiconductor device 400.
The semiconductor device 400 of this embodiment can include a printed wiring board 300 and a semiconductor element mounted on the circuit layer of the printed wiring board 300 or built in the printed wiring board 300.

For example, the semiconductor device 400 shown in FIG. 3A has a structure in which the semiconductor element 407 is mounted on the circuit layer (metal layer 303) of the printed wiring board 300 shown in FIG. On the other hand, the semiconductor device 400 shown in FIG. 3B has a structure in which the semiconductor element 407 is mounted on the circuit layer (metal layer 303) of the printed wiring board 300 shown in FIG. The semiconductor element 407 is covered with a sealing material layer 413. Such a semiconductor package may have a flip chip structure in which the semiconductor element 407 is electrically connected to the printed wiring board 300 via the solder bump 410 and the metal layer 303.

In the present embodiment, the structure of the semiconductor package is not limited to the flip chip connection structure, and may have various structures. For example, a fan-out structure may be used. The insulating layer formed from the cured resin film of the present embodiment can suppress substrate warpage and substrate cracks in the manufacturing process of the semiconductor package having a fan-out structure.

Next, a modified example of the printed wiring board of this embodiment will be described. 4A to 4C are process sectional views showing an example of a manufacturing process of the printed wiring board 500. FIG. As shown in FIG. 4C, the printed wiring board 500 of the present modification is a printed wiring board that does not have a core layer.
The printed wiring board 500 of the present embodiment can be a coreless resin substrate that is not provided with a core layer having a fiber base material, and is constituted by, for example, a buildup layer or a solder resist layer. These build-up layers and solder resist layers are preferably composed of an insulating layer formed from a cured product of the resin film of the present embodiment. For example, the printed wiring board 500 shown in FIG. 4C includes two build-up layers (insulating layers 540 and 550) and a solder resist layer (insulating layer 560). Note that the build-up layer of the printed wiring board 500 may be a single layer or may have two or more layers.

Since the insulating layer formed from the cured resin film of this embodiment is excellent in toughness, warpage of the printed wiring board 500 and cracks during transportation can be suppressed.

The metal layers 542, 552, and 562 shown in FIG. 4C may be circuit patterns, electrode pads, or may be formed by the SAP method as described above. . These metal layers 542, 552, and 562 may be a single layer or a plurality of metal layers.

The printed wiring board 500 may have a large area on which a plurality of semiconductor elements can be mounted on a plane. As a result, a plurality of semiconductor packages can be obtained by collectively sealing a plurality of semiconductor elements mounted on the printed wiring board 500 and then separating them into individual pieces. The printed wiring board 500 can be a panel board having a substantially circular shape or a rectangular shape.

The method for manufacturing the printed wiring board 500 is not particularly limited. For example, the printed wiring board 500 can be obtained by forming the buildup layer and the solder resist layer on the support substrate 510 and then peeling the support substrate 510. Specifically, as shown in FIG. 4A, a carrier foil 520 and a metal foil 530 (for example, copper foil) are arranged on a large-area support substrate 510 (for example, a plate member made of SUS). To do. At this time, an adhesive resin (not shown) can be provided between the support substrate 510 and the carrier foil 520. Subsequently, a metal layer 542 is formed on the metal foil 530. The metal layer 542 is patterned by a normal method such as an SAP method. Subsequently, after laminating the above resin film with a carrier film by a heating and pressing method or the like, the carrier substrate is peeled from the resin film with a carrier film. Then, the resin film is cured. These are repeated three times to form two build-up layers and one solder resist layer.
Thereafter, the support substrate 510 is peeled off as shown in FIG. Then, the metal foil 530 is removed by etching or the like.
Thus, the printed wiring board 500 shown in FIG. 4C is obtained.

Next, a modified example of the printed wiring board of this embodiment will be described. FIG. 5 is a cross-sectional view showing an example of the configuration of the printed wiring board 600.
A printed wiring board 600 shown in FIG. 5 may be composed of a coreless resin substrate 610 used in a PLP (panel level package) process. In the PLP process, for example, a panel size package having a larger area than a wafer can be obtained by using a wiring board process. By using the PLP process, the productivity of the semiconductor package can be improved more efficiently than the wafer level process.

In the present embodiment, the insulating layer 612 (interlayer insulating layer) and the insulating layers 630 and 632 (solder resist layer) of the coreless resin substrate 610 are configured by insulating layers formed from the cured resin film of the present embodiment. May be. Since the cured product of the resin film of this embodiment is excellent in toughness, it effectively suppresses warpage of the printed wiring board 600 and cracks of the coreless resin board 610 especially during transportation and mounting during the PLP process. be able to.

Further, the printed wiring board 600 of the present embodiment has a large area in which a plurality of semiconductor elements (not shown) can be mounted in the plane. Then, after sealing a plurality of semiconductor elements mounted in the in-plane direction of the printed wiring board 600 together, a plurality of semiconductor packages can be obtained by separating them into individual pieces. In this embodiment, since the linear expansion coefficient of the cured product of the resin film can be lowered, package warpage can be suppressed in the semiconductor package obtained by the PLP process.

The printed wiring board 600 can include a coreless resin substrate 610 and a solder resist layer (insulating layers 630 and 632) formed on the surface thereof. The coreless resin substrate 610 may have a built-in semiconductor element 620. The semiconductor element 620 can be electrically connected through the via wiring 616. The coreless resin substrate 610 can have at least an insulating layer 612 (interlayer insulating layer) and a via wiring 616. Via the via wiring 616, the lower metal layer 640 (electrode pad) and the upper metal layer 618 (post) can be electrically connected. Further, the via wiring 616 can be connected to the metal layer 640 via the metal layer 614 (post), for example. In the coreless resin substrate 610, a via wiring 616 and a metal layer 614 are embedded. The metal layer 614 that is a post may have a surface that is flush with the surface of the coreless resin substrate 610. In the printed wiring board 600 of the present embodiment, the coreless resin substrate 610 is configured by a single interlayer insulating layer, but is not limited to this configuration, and has a structure in which a plurality of interlayer insulating layers are stacked. May be. In such an interlayer insulating layer, at least a via wiring 616 may be formed as an interlayer connection wiring. In the present embodiment, the via wiring 616, the metal layer 614, or the metal layer 618 may be made of a metal such as copper, for example.

Further, the upper and lower surfaces of the coreless resin substrate 610 may be covered with a solder resist layer (insulating layers 630 and 632). For example, the insulating layer 630 can cover the metal layer 650 formed on the surface of the insulating layer 612. The metal layer 650 includes a first metal layer 652 (plating layer) and a second metal layer 654 (electroless plating layer), and may be a metal layer formed by the SAP method, for example. The metal layer 650 may be, for example, a circuit pattern or an electrode pad.

Moreover, the manufacturing method of the printed wiring board 600 of this embodiment is not specifically limited, For example, the following methods can be used. For example, the insulating layer 612 is formed over the supporting substrate. Subsequently, a via is formed in the insulating layer 612, and a metal film is embedded in the via by a plating method to form a via wiring 616. Subsequently, a rewiring (metal layer 650) is formed on the surface of the insulating layer 612 by the SAP method. Thereafter, a plurality of interlayer insulating layers having such interlayer connection wirings may be stacked. Thereafter, solder resist layers (insulating layers 630 and 632) are formed.
As described above, the printed wiring board 600 can be obtained.

Next, a modified example of the printed wiring board of this embodiment will be described. FIG. 6 is a cross-sectional view showing an example of the configuration of the printed wiring board 700.
A printed wiring board 700 shown in FIG. 6 can be formed of a substrate with a post (MIS substrate). For example, the post-attached substrate can be constituted by a coreless resin substrate 710 having a structure in which a via wiring 716 and a metal layer 718 (post) are embedded in an insulating layer 712 (interlayer insulating layer). The post-attached substrate may be a substrate after being singulated or a substrate having a large area before being singulated (for example, a support like a wafer).
By using the printed wiring board 700 of the present embodiment, the productivity of the semiconductor package can be efficiently improved to the same level as or higher than that of the wafer level process.

In the present embodiment, the insulating layer 712 (interlayer insulating layer) and the insulating layers 730 and 732 (solder resist layer) of the coreless resin substrate 710 are configured by insulating layers formed from the cured resin film of the present embodiment. May be. Since the cured product of the resin film of this embodiment is excellent in toughness, it is possible to effectively suppress warpage of the printed wiring board 700 and particularly cracks of the coreless resin substrate 710 during transportation and mounting.

In addition, the printed wiring board 700 of the present embodiment has a large area in which a plurality of semiconductor elements (not shown) can be mounted in the plane. Then, after sealing a plurality of semiconductor elements mounted in the in-plane direction of the printed wiring board 700 together, a plurality of semiconductor packages can be obtained by separating them into individual pieces. Since the linear expansion coefficient of the cured product of the resin film of this embodiment can be lowered, package warpage can be suppressed in the obtained semiconductor package.

The printed wiring board 700 can include a coreless resin substrate 710 and a solder resist layer (insulating layers 730 and 732) formed on the surface thereof. The coreless resin substrate 710 may have a built-in semiconductor element 720. The semiconductor element 720 can be electrically connected through the via wiring 716. The coreless resin substrate 710 can include at least an insulating layer 712 (interlayer insulating layer), a via wiring 716, and a metal layer 718 (post). The metal layer 714 (post) on the lower surface and the metal layer 718 (post) on the upper surface can be electrically connected via the via wiring 716. The metal layer 714 embedded in the insulating layer 712 can be connected to a metal layer 740 (electrode pad) formed on the surface of the insulating layer 712. Further, the surface of the insulating layer 712 may have a polished surface. One surface of the metal layer 718 may be flush with the polished surface of the insulating layer 712.

In the printed wiring board 700 of the present embodiment, the coreless resin substrate 710 is configured by a single interlayer insulating layer, but is not limited to this configuration, and has a structure in which a plurality of interlayer insulating layers are stacked. May be. In such an interlayer insulating layer, a via wiring 716 and a metal layer 718 (post) may be formed as an interlayer connection wiring. In the present embodiment, the via wiring 716, the metal layer 714, or the metal layer 718 may be made of a metal such as copper, for example. The upper and lower surfaces of the coreless resin substrate 710 may be covered with a solder resist layer (insulating layers 730 and 732).

Moreover, the manufacturing method of the printed wiring board 700 of this embodiment is not specifically limited, For example, the following methods can be used. For example, a copper post (eg, a metal layer 718) is formed over the insulating layer over the support substrate. A copper post is further embedded with an insulating layer. Subsequently, the surface of the copper post is exposed by a method such as grinding or chemical etching (that is, cueing of the copper post is performed). Subsequently, rewiring is formed by the SAP method. Through such a process, the coreless resin substrate 710 having an interlayer insulating layer can be formed. Thereafter, a plurality of interlayer insulating layers having interlayer connection wirings may be stacked by repeating the step of forming the interlayer insulating layer a plurality of times. Thereafter, solder resist layers (insulating layers 730 and 732) are formed.
Thus, the printed wiring board 700 can be obtained.

As described above, the embodiments of the present invention have been described with reference to the drawings. However, these are exemplifications of the present invention, and various configurations other than the above can be adopted.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the description of these examples.

(Preparation of thermosetting resin composition)
About the Example and the comparative example, the varnish-like thermosetting resin composition was adjusted.
First, each component was dissolved or dispersed at a solid content ratio shown in Table 1, adjusted with methyl ethyl ketone so as to have a nonvolatile content of 70% by weight, and stirred using a high-speed stirring device to prepare a resin varnish.
In addition, the numerical value which shows the mixture ratio of each component in Table 1 has shown the mixture ratio (weight%) of each component with respect to the whole solid content of a thermosetting resin composition.
The detail of the raw material of each component in Table 1 is as follows.

In the examples and comparative examples, the following raw materials were used.
(Thermosetting resin)
Thermosetting resin 1: bisphenol A type epoxy resin (DIC Corporation, EPICLON, 840S)
Thermosetting resin 2: In the following formula (1), a maleimide compound (BMI-) in which n ₁ is 0 or more and 3 or less, X ₁ is a group represented by “—CH ₂ —”, a is 0, and b is 0 2300, manufactured by Daiwa Kasei Kogyo, Mw = 750)

Thermosetting resin 3: Aralkyl epoxy resin (NC3000, manufactured by Nippon Kayaku Co., Ltd.)
Thermosetting resin 4: p-xylene-modified naphthol aralkyl-type cyanate resin represented by the following general formula (II) (naphthol aralkyl-type phenol resin (“SN-485 derivative” manufactured by Tohto Kasei Co., Ltd.) and cyan chloride)

(Benzoxazine compound)
Benzoxazine compound 1: A benzoxazine compound represented by the following formula obtained by the following production method.
Bisphenol A 1140 g and toluene 920 g were added to a flask equipped with a thermometer, a stirrer, a condenser, and a dropping device, and heated to 50 ° C. with stirring to dissolve bisphenol A. Thereafter, 652 g of formaldehyde was added to the flask. While further stirring these mixed liquids, 570 g of allylamine was dropped into the flask over 1 hour so that the temperature became 78 to 80 ° C. after 1 hour. After reacting for 7 hours under reflux, the benzoxazine compound 1 containing an allyl group was obtained by removing condensed water and reducing the pressure under the conditions of 100 ° C. and a pressure of 360 mmHg (about 48 kPa).

Benzoxazine compound 2: A bis-F benzoxazine compound represented by the following formula obtained by the following production method.
In a flask equipped with a thermometer, stirrer, condenser and dropping device, 139 g (0.5 mol) of 4,4′-diamino-3,3′-diallyldiphenylmethane, 94 g (1.0 mol) of phenol and n- 150 mL of butanol was added and heated to 60 ° C. with stirring to dissolve the solid components uniformly. Thereafter, 128 g (2.0 mol) of a 50% formalin solution was dropped into the flask over 10 minutes. These mixed liquids were reacted for 3 hours under reflux at 95 ° C. with further stirring, and then allyl groups were removed by removing condensed water and reducing pressure at 110 ° C. and a pressure of 360 mmHg (about 48 kPa). The contained benzoxazine compound 2 was obtained.

Benzoxazine compound 3: a bis-A type benzoxazine compound represented by the following formula obtained by the following production method.
Diallyl bisphenol A 1540 g and toluene 920 g were added to a flask equipped with a thermometer, a stirrer, a condenser and a dropping device, and heated to 50 ° C. with stirring to dissolve diallyl bisphenol A. Thereafter, 652 g of formaldehyde was added to the flask. While stirring these mixed liquids, 930 g of aniline was added dropwise to the flask over 1 hour so that the temperature became 78 to 80 ° C. after 1 hour. After reacting under reflux for 7 hours, benzoxazine compound 3 containing an allyl group was obtained by removing condensed water and reducing pressure under the conditions of 100 ° C. and a pressure of 360 mmHg (about 48 kPa).

Benzoxazine compound 4: A benzoxazine compound represented by the following formula obtained by the following production method.
Bisphenol F 1000 g and toluene 920 g were added to a flask equipped with a thermometer, a stirrer, a condenser, and a dropping device, and heated to 50 ° C. with stirring to dissolve bisphenol F. Thereafter, 652 g of formaldehyde was added to the flask. While stirring these mixed liquids, 1330 g of 2-allylaniline was added dropwise over 1 hour, and the temperature was adjusted to 78 to 80 ° C. after 1 hour. After reacting under reflux for 7 hours, the condensed water was removed and the pressure was reduced under the conditions of 100 ° C. and a pressure of 360 mmHg (about 48 kPa) to obtain an benzoxazine compound 4 containing an allyl group.

Benzoxazine compound 5: A benzoxazine compound represented by the following formula (Pd-type benzoxazine manufactured by Shikoku Kasei Co., Ltd.).

Benzoxazine compound 6: A benzoxazine compound represented by the following formula obtained by the following production method.
Bisphenol A 1140 g and toluene 920 g were added to a flask equipped with a thermometer, a stirrer, a condenser, and a dropping device, and heated to 50 ° C. with stirring to dissolve bisphenol A. Thereafter, 652 g of formaldehyde was added to the flask. While stirring these mixed liquids, 711 g of 2-methylallylamine was added dropwise over 1 hour so that the temperature became 78 to 80 ° C. after 1 hour. After reacting for 7 hours under reflux, removal of condensed water and reduced pressure were performed under conditions of 100 ° C. and a pressure of 360 mmHg (about 48 kPa) to obtain a benzoxazine compound 6 containing an allyl group having 4 carbon atoms. .

Benzoxazine compound 7: A benzoxazine compound represented by the following formula obtained by the following production method.
Bisphenol A 1140 g and toluene 920 g were added to a flask equipped with a thermometer, a stirrer, a condenser, and a dropping device, and heated to 50 ° C. with stirring to dissolve bisphenol A. Thereafter, 652 g of formaldehyde was added to the flask. While stirring these mixed liquids, 2675 g of oleylamine was added dropwise over 1 hour so that the temperature became 78 to 80 ° C. after 1 hour. After reacting under reflux for 7 hours, benzoxazine compound 7 containing an allyl group having 18 carbon atoms was obtained by removing condensed water and reducing the pressure under the conditions of 100 ° C. and a pressure of 360 mmHg (about 48 kPa). .

(Inorganic filler)
Inorganic filler 1: Silica particles (manufactured by Admatech, SC2050, average particle size 0.5 μm)
(Curing accelerator)
Curing accelerator 1: Phosphorus catalyst of an onium salt compound corresponding to the above formula (2) (C05-MB, manufactured by Sumitomo Bakelite Co., Ltd.)
Curing accelerator 2: 2-phenylimidazole (manufactured by Shikoku Kasei Co., Ltd., 2PZ-PW)
(Coupling agent)
Coupling agent 1: Silane coupling agent (N-phenyl γ-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573)

(Resin film with carrier)
In Examples and Comparative Examples, the obtained resin varnish was applied on a PET film as a carrier substrate, and then the solvent was removed at 140 ° C. for 2 minutes to form a resin film having a thickness of 25 μm. Thereby, a resin film with a carrier was obtained.
(Resin substrate)
In Examples and Comparative Examples, the obtained resin film with a carrier is cured under conditions of 180 ° C. for 2 hours, whereby a cured product of the resin film formed from the thermosetting resin composition is obtained as an insulating layer. A resin substrate was prepared.

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

(Prepreg)
In the examples and comparative examples, the obtained resin varnish was impregnated with a glass woven fabric (cross type # 2118, T-glass, basis weight 114 g / m ² ) with a coating apparatus, and dried with a hot air drying apparatus at 140 ° C. for 10 minutes. Thus, a prepreg having a thickness of 107 μm was obtained.

(Metal-clad laminate)
Ultra-thin copper foil (Mitsui Metal Mining Co., Ltd., Microcin Ex, 2.0 μm) is superposed on both surfaces of the prepregs obtained in the examples and comparative examples, and heated and pressure-molded at a pressure of 4 MPa and a temperature of 180 ° C. for 2 hours. As a result, a metal-clad laminate was obtained. The thickness of the core layer (portion formed by the resin substrate) of the obtained metal-clad laminate (resin substrate with metal foil) was 0.107 mm.

(Printed circuit board)
The ultrathin copper foil layer on the surface of the metal-clad laminate obtained in the examples and comparative examples was subjected to a roughening treatment of about 1 μm, and then a through hole of φ80 μm for interlayer connection was formed with a carbon dioxide laser. Next, it is immersed in a 60 ° C. swelling liquid (Atotech Japan, Swelling Dip Securigant P) for 5 minutes, and further immersed in an 80 ° C. aqueous potassium permanganate solution (Atotech Japan, Concentrate Compact CP) for 2 minutes. Then, it neutralized and the desmear process in a through hole was performed. Next, electroless copper plating was performed at a thickness of 0.5 μm, a resist layer for electrolytic copper plating was formed at a thickness of 18 μm, pattern copper plating was performed, and post-curing was performed by heating at a temperature of 150 ° C. for 30 minutes. Next, the plating resist was removed and the entire surface was flash etched to form a pattern of L / S = 15/15 μm.

In the examples and comparative examples, the following evaluations were performed on the laminated board and the printed wiring board. The evaluation results are shown in Table 3.

Below, the specific content of each evaluation item shown in Table 2 and Table 3 is demonstrated.
(Average linear expansion coefficient (30 ℃ -240 ℃))
Cured product used for resin substrate:
Four resin films from which the PET film, which is a carrier substrate, was peeled off from the resin film with carrier obtained in the examples and comparative examples were laminated to prepare a resin sheet having a thickness of 100 μm. Next, the resin sheet was heat treated at 180 ° C. for 2 hours to obtain a cured product.
Hardened material used for metal-clad laminates:
The copper foil was removed from the metal-clad laminates obtained in Examples and Comparative Examples with an etching solution (ferric chloride solution, 35 ° C.) to obtain a cured product of prepreg.
Measurement of linear expansion coefficient:
A test piece having a measurement length of 6 mm × 6 mm is cut out from the cured product used for the resin substrate or the metal-clad laminate, and a thermomechanical analyzer TMA (manufactured by TA Instruments, Q400) is used for the test piece. Thermomechanical analysis (TMA) was measured for two cycles under the conditions of a temperature range of 30 to 300 ° C., a heating rate of 10 ° C./min, a load of 10 g and a compression mode. Average value of linear expansion coefficient in the plane direction (XY direction) in the range of 30 ° C to 240 ° C, average value α1 (CETα1) of linear expansion coefficient in the plane direction (XY direction) in the range of 30 ° C to 150 ° C, and 150 ° C The average value α2 (CETα2) of the linear expansion coefficient in the plane direction (XY direction) in the range of ˜240 ° C. was calculated. In addition, the value of the 2nd cycle was employ | adopted for the linear expansion coefficient.

(Peel strength)
Using the metal-clad laminates obtained in the examples and comparative examples, the peel strength between the cured prepreg and the metal foil, measured according to JIS C-6481: 1996, was measured under HAST conditions (temperature 130 Measured after treatment for 100 hours at a temperature of 85 ° C. and a humidity of 85%.

(Glass-transition temperature)
The glass transition temperature was measured using dynamic viscoelasticity measurement (DMA device, manufactured by TA Instruments, Q800) under the following conditions.
Four resin films from which the PET film, which is a carrier substrate, was peeled off from the resin film with carrier obtained in the examples and comparative examples were laminated to prepare a resin sheet having a thickness of 100 μm. Next, the resin sheet was heat treated at 180 ° C. for 2 hours to obtain a cured product.
A test piece of 8 mm × 40 mm was cut out from the obtained cured product, and dynamic viscoelasticity measurement was performed on the test piece at a heating rate of 5 ° C./min and a frequency of 1 Hz.
Here, the glass transition temperature was a temperature at which the loss tangent tan δ showed the maximum value.

(Panel warpage)
A 12 μm copper foil is placed on a support substrate of length 250 mm × width 250 mm square SUS, and a resin film with a carrier film obtained in Examples and Comparative Examples is a two-stage vacuum / pressure laminator (manufactured by Meiki Seisakusho, MVLP-500), the pressure was reduced to 30 h for 10 seconds or less at a temperature of 120 ° C. and a pressure of 0.8 MPa for 30 seconds as a one-stage condition, and then a temperature of 120 ° C. with a SUS end plate as a two-stage condition. Vacuum heating and pressing were performed under conditions of a pressure of 1.0 MPa and 60 seconds. Next, the carrier substrate was peeled from the resin film with carrier, and then cured at 180 ° C. for 2 hours. The above process was repeated three times to form a three-layer buildup layer, and the warpage of the panel when SUS peeled was evaluated by measuring the warpage of the plate edge.
A: Less than 15 mm B: 15 mm or more and less than 50 mm (substantially no problem)
C: 50 mm or more

(Handling properties)
About the three-layer buildup layer obtained in the Examples and Comparative Examples, 12 μm copper foil was further etched after SUS peeling. Thereafter, the presence or absence of cracks in the panel was evaluated.
A: No crack B: Crack

(Interlayer insulation reliability)
A double-sided copper-clad laminate (manufactured by Sumitomo Bakelite Co., Ltd., LαZ-4785GH-J) prepared by laminating copper foils having a thickness of 12 μm was prepared. Subsequently, the copper foil of the said copper clad laminated board was etched, and the conductor circuit pattern was formed, and the circuit board by which the said conductor circuit pattern was formed in the one surface and the other surface was obtained. Next, the resin film with a carrier film obtained in Examples and Comparative Examples was decompressed for 30 seconds using a two-stage vacuum / pressure laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.), and one stage at 10 hPa or less. After processing under conditions of a temperature of 120 ° C. and a pressure of 0.8 MPa for 30 seconds, vacuum heating and press molding was performed with a SUS end plate under the conditions of a temperature of 120 ° C. and a pressure of 1.0 MPa for 60 seconds as a two-stage condition. Next, after peeling the carrier substrate from the resin film with carrier, a 12 μm thick copper foil was laminated under the same conditions, and then cured at 180 ° C. for 2 hours. An outer layer pattern of the obtained multilayer wiring board was formed to produce an insulation reliability evaluation sample having an interlayer thickness of 20 μm. 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 3.3 V. A resistance value of 10 ⁶ Ω or less was regarded as a failure. The evaluation criteria are as follows.
A: No failure for 500 hours or more (good)
B: There is a failure in 200 hours or more and less than 500 hours (substantially no problem)
C: There is a failure in 100 hours or more and less than 200 hours (substantially unusable)
D: Failure in less than 100 hours (cannot be used)

(Hygroscopic solder heat resistance test)
Using the same sample as the insulation reliability evaluation sample prepared in the above-described evaluation of interlayer insulation reliability, the presence or absence of swelling was confirmed by repeating 30 ° C. solder immersion for 30 seconds after PCT 24h. In addition, in place of the double-sided copper-clad laminate, except for the use of the obtained metal-clad laminate, evaluation was also made on samples similar to the insulation reliability evaluation samples prepared in the evaluation of interlayer insulation reliability. went.
A: No swelling even after 11 times (good)
B: Swells 5 to 10 times (substantially no problem)
C: Swells 2 to 5 times (not practically usable)
D: Swells once (cannot be used)

(Through hole insulation reliability evaluation)
In the production of 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 (BLA-3700GS, manufactured by Sumitomo Bakelite Co., Ltd.) was laminated and cured on the circuit pattern was produced. Using this test sample, the insulation resistance in continuous humidity was evaluated under the conditions of a temperature of 130 ° C., a humidity of 85%, and an applied voltage of 5.5V. A resistance value of 10 ⁶ Ω or less was regarded as a failure. The evaluation criteria are as follows.
A: No failure for 500 hours or more (good)
B: There is a failure in 200 hours or more and less than 500 hours (substantially no problem)
C: There is a failure in 100 hours or more and less than 200 hours (substantially unusable)
D: Failure in less than 100 hours (cannot be used)

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

As described above, the present invention has been described more specifically based on the embodiments. However, these are exemplifications of the present invention, and various configurations other than the above can be adopted.

The thermosetting resin composition of the present invention includes the benzoxazine compound represented by the general formula (B-1) or (B-2) described above and at least one of a maleimide compound, an epoxy resin, and a cyanate resin. And an inorganic filler. Such a thermosetting resin composition can lower the linear expansion coefficient of the obtained cured product. Therefore, an insulating layer excellent in low warpage can be obtained by using such a thermosetting resin composition. Moreover, a resin film with a carrier, a prepreg, a metal-clad laminate, a resin substrate, a printed wiring board, and a semiconductor device using such an insulating layer can be obtained. Therefore, the present invention has industrial applicability.

Claims

A thermosetting resin composition used for forming an insulating layer in a printed wiring board,
A benzoxazine compound represented by the following general formula (B-1) or (B-2);
A thermosetting resin containing at least one of a maleimide compound, an epoxy resin and a cyanate resin;
And a thermosetting resin composition comprising an inorganic filler.

(In the general formula (B-1), a independently represents an integer of 1 to 3, and p represents an integer of 1 to 4. R 1 and R 2 each independently represents a hydrogen atom, Represents a lower alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a monovalent to tetravalent organic group, wherein at least one of R 1 and R 2 represents an alkenyl group having 3 to 14 carbon atoms. (However, when p is an integer of 2 or more and 4 or less, R 2 may be the same or different.) Z represents a monovalent to tetravalent organic group.)

(In the above general formula (B-2), each b independently represents an integer of 1 or more and 4 or less, q represents an integer of 1 or more and 4 or less. R 3 independently represents a hydrogen atom or lower alkyl. Group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a monovalent to tetravalent organic group, and X 1 represents a monovalent to tetravalent organic group, at least one of R 3 and X 1 One is a group having an alkenyl group having 3 to 14 carbon atoms.)
The benzoxazine compound represented by the general formula (B-1) has a structure represented by the following general formula (B-3),
The thermosetting resin composition according to claim 1, wherein the benzoxazine compound represented by the general formula (B-2) has a structure represented by the following general formula (B-4).

(In the above general formula (B-3), Z represents a direct bond, an alkylene group having 1 to 10 carbon atoms, C═O, O, S, S═O or O═S═O. R 1 and R At least one of 2 is a group having an alkenyl group having 3 to 14 carbon atoms.

(In the general formula (B-4), c each independently represents an integer of 1 to 4, X 2 represents a direct bond, an alkylene group having 1 to 10 carbon atoms, C═O, O, S, S = O or O = S = O. R is a group having an alkenyl group having 3 to 14 carbon atoms.
The thermosetting resin composition according to claim 1 or 2, wherein the group having an unsaturated double bond is an allyl group.
The thermosetting resin composition according to any one of claims 1 to 3, wherein a content of the inorganic filler is 50% by weight or more and 90% by weight or less with respect to the entire thermosetting resin composition.
When a thermomechanical analysis is performed on the cured product of the thermosetting resin composition, the average linear expansion coefficient calculated in the range of 30 ° C. to 240 ° C. of the cured product is 1 ppm / ° C. to 40 ppm / ° C. The thermosetting resin composition according to any one of claims 1 to 4.
When thermomechanical analysis was performed on the cured product of the thermosetting resin composition, the average linear expansion coefficient calculated in the range of 30 ° C. to 150 ° C. of the cured product was α1, and 150 When the average linear expansion coefficient calculated in the range from ℃ to 240 ℃ is α2,
The thermosetting resin composition according to any one of claims 1 to 5, wherein an average linear expansion coefficient ratio (α2 / α1) is 0.7 or more and 3.0 or less.
The thermosetting resin composition according to any one of claims 1 to 6, wherein a peel strength of the cured product of the thermosetting resin composition with respect to the copper foil is 0.5 kN / m or more.
The thermosetting resin composition according to any one of claims 1 to 7, wherein a glass transition temperature of a cured product of the thermosetting resin composition is 140 ° C or higher.
The thermosetting resin composition according to any one of claims 1 to 8, wherein the inorganic filler contains silica.
A carrier substrate;
A resin film formed from the thermosetting resin composition according to any one of claims 1 to 9, which is provided on the carrier base material.
A prepreg formed by impregnating a fiber base material with the thermosetting resin composition according to any one of claims 1 to 9.
A metal-clad laminate comprising the cured product of the prepreg according to claim 11 and a metal layer disposed on at least one surface of the cured product.
A resin substrate comprising an insulating layer made of a cured product of the thermosetting resin composition according to any one of claims 1 to 9.
A printed wiring board comprising: the metal-clad laminate according to claim 12 or the resin substrate according to claim 13; and a circuit layer formed on a surface of the metal-clad laminate or the resin substrate. .
A printed wiring board according to claim 14,
A semiconductor device comprising: a semiconductor element mounted on a circuit layer of the printed wiring board or built in the printed wiring board.