JP2019163365A - Thermosetting resin composition, resin film with carrier, prepreg, metal-clad laminate, printed wiring board and semiconductor device - Google Patents

Abstract

To provide a thermosetting resin composition capable of obtaining an insulation layer excellent in heat resistance and low water absorption.SOLUTION: A thermosetting resin composition is used for forming an insulation layer in a printed wiring board, and contains a polyfunctional phenol resin including an aldehyde group and a functional group that reacts the aldehyde group and is different from the aldehyde group in one molecule, and an inorganic filler, in which a content of the inorganic filler to 100 wt.% of the total solid content of the thermosetting resin composition is 50 wt.% or more and 90 wt.% or less, and an average particle size of the inorganic filler is 0.01 μm or more and 5.0 μm or less.SELECTED DRAWING: Figure 1

Description

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

  So far, various developments have been made on thermosetting resin compositions in the electric and electronic fields. As this type of technology, for example, a thermosetting resin composition described in Patent Document 1 is cited. According to this document, a thermosetting resin composition containing a biphenyl aralkyl type epoxy resin and a biphenyl aralkyl type phenol resin is described (Example 1 of Patent Document 1).

JP 2004-346101 A

  However, the cured product of the thermosetting resin composition described in the above document has been found to have room for improvement in terms of heat resistance and low water absorption.

  The present inventor further examined the thermosetting resin composition used for forming the insulating layer in the printed wiring board, and focuses on heat resistance and low water absorption among the physical properties of the cured product of the thermosetting resin composition. It came to. As a result of examination based on such a point of interest, the following knowledge was obtained. That is, as described in the above-mentioned document 1, when a biphenyl aralkyl type epoxy resin and a biphenyl aralkyl type phenol resin are used in combination, the glass transition temperature becomes relatively low, so that the heat resistance may be lowered. On the other hand, in order to increase the glass transition temperature (Tg), when a means for using a polyfunctional epoxy resin and a polyfunctional phenol resin together is adopted as a means for increasing the crosslinking point between the epoxy resin and the phenol resin, the Tg is high. However, it has been found that the water absorption rate is increased. Although the detailed mechanism is not clear, it is considered that in a design that simply increases the crosslinking point of the cured product, the free volume increases and the water absorption rate increases.

  Based on these findings, further diligent research has revealed that by adopting a polyfunctional phenol resin having different functional groups that react with each other in the molecule, the Tg of the cured product can be increased and the water absorption can be decreased. Therefore, the present inventors have found that a thermosetting resin composition capable of obtaining an insulating layer excellent in heat resistance and low water absorption can be realized, and the present invention has been completed.

According to the present invention,
A thermosetting resin composition used for forming an insulating layer in a printed wiring board,
A polyfunctional phenol resin comprising, in one molecule, an aldehyde group and a functional group that reacts with the aldehyde group and is different from the aldehyde group;
An inorganic filler,
Content of the said inorganic filler with respect to 100 weight% of total solid of the said thermosetting resin composition is 50 to 90 weight%, and the average particle diameter of the said inorganic filler is 0.01 to 5.0 micrometer. The following thermosetting resin composition is provided.

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

  Moreover, according to this invention, the prepreg formed by impregnating the said thermosetting resin composition in a fiber base material is provided.

  The present invention also provides a metal-clad laminate in which a metal layer is disposed on at least one surface of the cured product of the prepreg.

  Moreover, according to this invention, the printed wiring board by which the circuit layer was formed in the surface of the said metal-clad laminated board 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 heat resistance and low water absorption, a resin film with a carrier, a metal-clad laminate, a printed wiring board, and a semiconductor device using the same. The

It is sectional drawing which shows an example of a structure of the resin film with a carrier in this embodiment. It is sectional drawing which shows an example of a structure of the printed wiring board in this embodiment. It is sectional drawing which shows an example of a structure of the semiconductor device in this embodiment. It is process sectional drawing which shows an example of the manufacturing process of the printed wiring board in this embodiment. It is sectional drawing which shows an example of a structure of the printed wiring board in this embodiment. It is sectional drawing which shows an example of a structure of the printed wiring board in this 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, in one molecule, a polyfunctional phenol resin that includes an aldehyde group and a functional group that reacts with the aldehyde group and is different from the aldehyde group, And an inorganic filler. Such a thermosetting resin composition is used for forming an insulating layer in a printed wiring board.

As a result of the study of the thermosetting resin composition by the present inventors, when a biphenyl aralkyl type epoxy resin and a biphenyl aralkyl type phenol resin are used in combination, the glass transition temperature becomes relatively low, while the polyfunctional epoxy resin When a functional phenol resin was used in combination, these cross-linking points increased, so that the Tg was increased, but the water absorption was also increased.
Although the detailed mechanism is not clear, a design that simply increases the cross-linking point of the cured product is considered to increase the free volume of the cured product and increase the water absorption rate.
Therefore, as a result of further investigation on the crosslinked structure, the present inventor can increase the Tg and decrease the water absorption rate by adopting a polyfunctional phenol resin having different functional groups that react with each other in the molecule. I found. Although the detailed mechanism is not clear, it is thought that water absorption is suppressed by the optimal cross-linking structure while different functional groups different from each other react between the molecules of the polyfunctional phenol resin to increase the cross-linking points.

According to the thermosetting resin composition of the present embodiment, the Tg of the cured product can be increased,
The heat resistance of the insulating layer in the printed wiring board can be improved. Thereby, for example, since the swelling of the insulating layer at a high temperature can be suppressed, the warpage of the substrate can be reduced and the substrate reliability can be improved. Moreover, according to the thermosetting resin composition of this embodiment, since the water absorption rate of hardened | cured material can be made low, the insulating layer excellent in the low water absorption is realizable. Thereby, for example, since the moisture content that is one of the factors of swelling is small, the occurrence of swelling and the like can be suppressed, and the substrate reliability can be improved.
Therefore, by using the thermosetting resin composition of the present embodiment, a printed wiring board or a semiconductor device having a structure excellent in substrate reliability can be realized.

  In the present 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), and a solder resist layer. 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 made of the thermosetting resin composition of the present embodiment is used for the insulating layer, for example, a build-up layer, a solder resist layer, or a PLP in a printed wiring board having no core layer. It can also be used for the interlayer insulating layer and solder resist layer of the coreless substrate used, the interlayer insulating layer and solder resist layer of the MIS substrate, and the like. 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, according to this embodiment, since the linear expansion coefficient of the hardened | cured material of a thermosetting resin composition can be made low, the curvature of the semiconductor package obtained can fully be suppressed.

  Each component of the thermosetting resin composition of this embodiment is demonstrated.

  The thermosetting resin composition of this embodiment can contain a polyfunctional phenol resin and an inorganic filler.

(Multifunctional phenolic resin)
In the present embodiment, as the polyfunctional phenol resin, for example, a polyfunctional phenol resin having an aldehyde group and a functional group different from the aldehyde group in one molecule can be used. The aldehyde group may be directly bonded to the aromatic ring of the polyfunctional phenol resin, or may be bonded singly or in combination to one aromatic ring. The functional group may be directly bonded to the aromatic ring of the polyfunctional phenol resin (however, the aldehyde group is not bonded), or may be bonded to the aromatic ring singly or in combination. Good.

  As a functional group in the said polyfunctional phenol resin, the functional group which reacts with the aldehyde group in a molecule | numerator can be used, For example, an imino group etc. can be used. In the present embodiment, the imino group is not particularly limited as long as it has a carbon-nitrogen double bond, and may be represented, for example, by a structure of —CH═N—R. As such R, for example, an alkyl group, an alkenyl group, or an alkoxy group having 1 to 9 carbon atoms can be used as long as it is linear or branched. An aromatic structure such as a group may be included. An alkenyl group may be preferably used, and an alkenyl group having 3 carbon atoms may be more preferably used.

  Moreover, as said polyfunctional phenol resin, the polyfunctional phenol resin which has biphenyl frame | skeleton can be included, for example. Thereby, the water absorption of the hardened | cured material obtained can be reduced.

Moreover, as said polyfunctional phenol resin, the compound represented by a following formula can be included.

  In the above formula, Y and Z represent any of the aldehyde group, the imino group, and a hydrogen atom, a and b each represent an integer of 1 to 3, and X represents a divalent aromatic group. Hereinafter, “to” represents that an upper limit value and a lower limit value are included unless otherwise specified. In the present embodiment, a and b may each be 1. Moreover, n represents a repeating unit, for example, is an integer of 1-10. X, Z and b contained in each repeating unit may be the same or different. However, at least one aldehyde group and imino group are contained in Y and Z in the repeating unit.

In the above general formula, the divalent aromatic group as X may be any group having an aromatic ring such as a benzene ring or a naphthalene ring.
The divalent aromatic group represented by X in the formula means a substituent having an aromatic ring, and has one or more aromatic rings, and the aromatic ring is C, H, O And a group composed of N and the like. Specifically, it is preferable to have a structure represented by the following formula.

  Among these, as said X, a biphenylene group and a xylylene group are preferable, and a 4,4'-biphenylene group and a paraxylylene group are more preferable.

  According to this embodiment, the phenolic hydroxyl group in the polyfunctional phenol resin can react with the epoxy group in the thermosetting resin such as an epoxy resin. Moreover, the aldehyde group and other functional group in the molecule | numerator of polyfunctional phenol resin can mutually react. Although the detailed mechanism is not clear, after reacting with the phenolic hydroxyl group and the epoxy group in other components to form a crosslinked structure, the aldehyde group and the imino group react further, and the crosslinked structure is thought to be further densified. It is done. For this reason, by using the polyfunctional phenol resin which concerns on this embodiment, the linear expansion coefficient of hardened | cured material can be reduced and it becomes possible to make a water absorption rate comparatively small, making Tg high.

(Thermosetting resin)
Moreover, the thermosetting resin composition of this embodiment can contain a thermosetting resin.
Examples of the thermosetting resin include an epoxy resin, a bismaleimide resin, a benzoxazine compound, and the like. Among these, the thermosetting resin may contain an epoxy resin or a bismaleimide resin. These may be used alone or in combination of two or more. In this embodiment, Tg can be further increased by using the polyfunctional phenol resin and a thermosetting resin including an epoxy resin in combination.

  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-phenylenediiso Pridiene) 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′-cyclohexyl) Diene bisphenol type epoxy resin), etc .; phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type novolac type epoxy resin, novo having a condensed ring aromatic hydrocarbon structure Novolac epoxy resins such as epoxy resins; biphenyl epoxy resins; aralkyl epoxy resins such as xylylene epoxy resins and biphenyl aralkyl epoxy resins (phenol aralkyl epoxy resins having a biphenylene skeleton); naphthylene ether epoxy Resin, naphthol type epoxy resin, naphthalene diol type epoxy resin, bifunctional to tetrafunctional naphthalene type epoxy resin, binaphthyl type epoxy resin, naphthalene aralkyl type epoxy resin, and the like; anthracene type epoxy resin; phenoxy type epoxy resin; Examples include dicyclopentadiene type epoxy resins; norbornene type epoxy resins; adamantane type epoxy resins; fluorene type epoxy resins.

  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 and those prepolymers 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 One or more selected from the group consisting of anthracene type epoxy resins and dicyclopentadiene type epoxy resins are preferred, and they are selected from aralkyl type epoxy resins, novolak type epoxy resins having a condensed ring aromatic hydrocarbon structure and naphthalene type epoxy resins. One or more selected from the group consisting of

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

  Among these epoxy resins, aralkyl type epoxy resins are particularly preferable. Thereby, the moisture absorption solder heat resistance and flame retardance of the cured product of the resin film can be further improved.

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

（上記一般式（１）中、ＡおよびＢは、ベンゼン環、ビフェニル構造等の芳香族環を表す。またＡおよびＢの芳香族環の水素が置換されていてもよい。置換基としては、例えば、メチル基、エチル基、プロピル基、フェニル基等が挙げられる。ｎは繰返し単位を表し、例えば、１〜１０の整数である。）

(In the above general formula (1), A and B represent an aromatic ring such as a benzene ring or a biphenyl structure. Hydrogen in the aromatic ring of A and B may be substituted. For example, a methyl group, an ethyl group, a propyl group, a phenyl group, etc. are mentioned, n represents a repeating unit, for example, is an integer of 1-10.)

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

（式（１ａ）中、ｎは、１〜５の整数を示す。）

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

（式（１ｂ）中、ｎは、１〜５の整数を示す。）

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

  As the epoxy resin other than the above, a novolak 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 obtained by epoxidizing a novolac 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 and 3,5-xylenol; Trimethylphenols such as 2,3,5 trimethylphenol; Ethyl such as o-ethylphenol, m-ethylphenol and 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-dihydroxynaphthalene , 2,7-naphthalene diols dihydroxy naphthalene; resorcinol, catechol, hydroquinone, pyrogallol, polyhydric phenols such as fluoro Guru Singh; alkylresorcin, alkylcatechol, alkyl polyhydric phenols and alkyl hydroquinone. Of these, phenol is preferable from the viewpoint of cost and the effect on the decomposition reaction.

  The aldehyde compound is 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.)
Further, 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 one having a naphthalene ring skeleton and having two or more glycidyl groups.
Further, 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 a naphthol type epoxy resin, for example, the following general formula (VII-1), as a naphthalene diol type epoxy resin, the following formula (VII-2), as a bifunctional or tetrafunctional naphthalene type epoxy resin, the following formula (VII-3) As (VII-4) (VII-5) and a naphthylene ether type epoxy resin, it can show by the following general formula (VII-6), for example.

（ｎは平均１以上６以下の数を示し、Ｒはグリシジル基または炭素数１以上１０以下の炭化水素基を示す。）

(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.)

（式中、Ｒ^１は水素原子またはメチル基を表し、Ｒ^２はそれぞれ独立的に水素原子、炭素原子数１〜４のアルキル基、アラルキル基、ナフタレン基、またはグリシジルエーテル基含有ナフタレン基を表し、ｏおよびｍはそれぞれ０〜２の整数であって、かつｏまたはｍの何れか一方は１以上である。）

(Wherein 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.)

  Although the lower limit of the weight average molecular weight (Mw) of an epoxy resin is not specifically limited, Mw300 or more may be sufficient, Preferably it is good also as Mw800 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 value of Mw is not particularly limited, but may be Mw 20,000 or less, and 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 60% by weight or less, for example, 45% by weight or less. More preferred is 30% 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.

(Bismaleimide compound)
The thermosetting resin composition of this embodiment can contain a bismaleimide compound.
The bismaleimide compound of this embodiment is a maleimide compound having at least two maleimide groups in the molecule.

  Moreover, as a bismaleimide compound, it is preferable that the bismaleimide compound shown by following formula (1) is included.

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

(In the above formula (1), n ₁ is an integer of 0 or more and 10 or less, 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)

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

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

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

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

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

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

R ₁ is independently a hydrocarbon group having 1 to 6 carbon atoms, 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 bismaleimide 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 and having an aromatic ring may be composed only of an aromatic ring or may have a hydrocarbon group other than the aromatic ring. Y may have one aromatic ring or two or more aromatic rings, and in the case of two or more, these aromatic rings may be the same or different. The aromatic ring may be a monocyclic structure or a polycyclic structure.

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

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

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

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

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

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

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

From the above, in the bismaleimide 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 carbonized. It is preferably a hydrogen group, 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 bismaleimide compound represented by the above formula (1), for example, a bismaleimide compound represented by the following formula (1-1) is particularly preferably used.

Further, the bismaleimide compound may contain a different type of bismaleimide compound from the bismaleimide compound represented by the above formula (1).
Such bismaleimide compounds include 1,6′-bismaleimide (2,2,4-trimethyl) hexane, hexamethylenediamine bismaleimide, N, N′-1,2-ethylene bismaleimide, N, N ′. Examples include aliphatic bismaleimide compounds such as -1,3-propylene bismaleimide and N, N′-1,4-tetramethylene bismaleimide; imide-expanded bismaleimide. Among these, 1,6′-bismaleimide (2,2,4-trimethyl) hexane and imide-extended bismaleimide are particularly preferable. A bismaleimide compound may be used independently and may use 2 or more types together.
Examples of the imide-extended bismaleimide include bismaleimide compounds represented by the following formula (a1), bismaleimide compounds represented by the following formula (a2), bismaleimide compounds represented by the following formula (a3), and the like. Can be mentioned. Specific examples of the bismaleimide compound represented by the formula (a1) include BMI-1500 (manufactured by Designa Molecules Co., Ltd., molecular weight 1500). Specific examples of the bismaleimide compound represented by the formula (a2) include BMI-1700 (manufactured by Designer Molecules, molecular weight 1700), BMI-1400 (manufactured by Diginer Molecules, molecular weight 1400), and the like. It is done. Specific examples of the bismaleimide compound represented by the formula (a3) include BMI-3000 (manufactured by Designa Molecules Co., Ltd., molecular weight 3000).

上記式（ａ１）において、ｎは１以上１０以下の整数を示す。

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

上記式（ａ２）において、ｎは１以上１０以下の整数を示す。

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

上記式（ａ３）において、ｎは１以上１０以下の整数を示す。

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

  The lower limit of the weight average molecular weight (Mw) of the bismaleimide 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 bismaleimide compound can be measured by, for example, GPC (gel permeation chromatography, standard substance: converted to polystyrene).

  As the bismaleimide compound, a reaction product of a bismaleimide compound and an amine compound can also 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, and 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- Phenyl methane, 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, and the like. It is done.

  The reaction between the bismaleimide 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 bismaleimide 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. Is preferably 1.0% by weight or more and 25.0% by weight or less, more preferably 3.0% by weight or more and 20.0% by weight or less. When the content of the bismaleimide compound is within the above range, the balance of low heat shrinkage and chemical resistance of the obtained insulating layer can be further improved.

  In the present embodiment, the “solid content of the thermosetting resin composition” refers to the non-volatile content in the thermosetting resin composition, and refers to the remainder excluding volatile components such as water and solvent. Moreover, in this embodiment, content with respect to the whole thermosetting resin composition points out content with respect to the whole solid content except the solvent of a thermosetting resin composition, when a solvent is included.

(Curing agent)
The thermosetting resin composition of the present embodiment can contain a curing agent.
Further, the curing agent of the present embodiment is not particularly limited. For example, a tertiary amine compound such as benzyldimethylamine (BDMA) or 2,4,6-trisdimethylaminomethylphenol (DMP-30); an imidazole compound; Examples thereof include catalytic curing agents such as Lewis acids such as BF ₃ complexes.
In addition, 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 (excluding the polyfunctional phenol resin); a urea resin such as a methylol group-containing urea resin; A condensation type curing agent such as a melamine resin such as a methylol group-containing melamine resin may also be used. These may be used alone or in combination of two or more.

The above-mentioned phenol resin-based curing agents are monomers, oligomers and polymers in general having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure thereof are not particularly limited. For example, phenol novolak resin, cresol Novolac type phenol resins such as novolak resin and naphthol novolak resin; polyfunctional type phenol resins such as triphenolmethane type phenol resin; modified phenol resins such as terpene modified phenol resin and dicyclopentadiene modified phenol resin; phenylene skeleton and / or biphenylene Aralkyl type resins such as phenol aralkyl resins having a skeleton (biphenyl aralkyl type phenol resins), phenylene and / or naphthol aralkyl resins having a biphenylene skeleton; Le A, bisphenol compounds such as bisphenol F and the like. These may be used alone or in combination of two or more. Of these, those having a hydroxyl equivalent weight of 90 g / eq or more and 250 g / eq or less may be used from the viewpoint of curability.
The weight average molecular weight of the phenol resin is not particularly limited, but may be a weight average molecular weight of 4 × 10 ^{2 to} 1.8 × 10 ³ , and 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. For example, it is preferably 25% by weight or less, more preferably 20% by weight or less. 15% 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.

  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. Is more preferable, and 0.2% by weight or more is more preferable. Thereby, the dispersibility of a (meth) acrylic-type block copolymer can fully be improved. 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. For example, it is preferably 25% by weight or less, more preferably 20% by weight or less. 15% by weight or less is more 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, it may be, for example, 0.01 μm or more, or 0.05 μm or more. 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 measured, for example, by measuring the particle size distribution on a volume basis with a laser diffraction particle size distribution measuring device (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 may be, for example, 5.0 μm or less, 0.1 μm or more and 4.0 μm or less, or 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 may be, for example, 90% by weight or less, and 85% by weight or less. Or 80% by weight or less. Thereby, the workability of the cured product of the resin film can be improved.

(Cyanate resin)
The thermosetting resin composition of the present embodiment can further contain a cyanate resin.
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 novolak 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 a novolak-type cyanate resin, what is shown by the following general formula (I) can be used, for example.

  The average repeating unit n of the novolak type 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 -It is 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 yield can be prevented from decreasing.

（式中、Ｒはそれぞれ独立に水素原子またはメチル基を示し、ｎは１以上１０以下の整数を示す。）

(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.)

  Moreover, cyanate resin may be used individually by 1 type, may use 2 or more types together, and may use 1 type, or 2 or more types, and those prepolymers together.

  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.

(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, what 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-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl- 4-methylimidazole, 2-ethyl-4-ethylimidazole, 2-phenyl-4-ethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-Phenyl-4,5-dihi Imidazoles such as loxyimidazole, 1-benzyl-2-phenylimidazole, 2-phenyl-1H-imidazole 4,5-dimethanol, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, phenol One or two or more selected from phenolic compounds such as bisphenol A and nonylphenol, organic acids such as acetic acid, benzoic acid, salicylic acid and paratoluenesulfonic acid, and onium salt compounds. 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 hardening accelerator is not specifically limited, For example, the compound represented by following General formula (2) can be used.

（上記一般式（２）中、Ｐはリン原子、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ、置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を示し、互いに同一であっても異なっていてもよい。Ａ⁻は分子外に放出しうるプロトンを少なくとも１個以上分子内に有するｎ（ｎ≧１）価のプロトン供与体のアニオン、またはその錯アニオンを示す）

(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 ⁻ represents an n (n ≧ 1) -valent proton donor anion having at least one proton that can be released to the outside of the molecule. Or a complex anion thereof)

  The lower limit of the content of the curing accelerator may be, for example, 0.01% by weight or more, preferably 0.05% by weight or more with respect to 100% by weight of the total solid content of the thermosetting resin composition. It is good. 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 of the content of the curing accelerator may be, for example, 2.5% by weight or less, preferably 1% by weight or less with respect to 100% by weight of the total solid content of the thermosetting resin composition. Good. 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.

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

  Specific examples of the compound include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-amino. Propylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (aminohexyl) 3-aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldimethoxysilane, β- (3,4- (Epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, γ-ureidopropyltriethoxysilane, vinyltriethoxysilane, etc., and a combination of one or more of these. Of these, epoxy silane, mercapto silane, and amino silane are preferable, and 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 may be, for example, 0.01% by weight or more, preferably 0.05% by weight with respect to 100% by weight of the total solid content of the thermosetting resin composition. It is good also as above. 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 may be, for example, 3% by weight or less, preferably 1.5% by weight or less, with respect to 100% by weight of the total solid content of the thermosetting resin composition. Good. 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)
In addition, the thermosetting resin composition of the present embodiment is not limited to the object of the present invention, and the dyes such as green, red, blue, yellow, and black, pigments such as black pigments, and the like, are formed from the group consisting of pigments. The above-mentioned components (thermosetting resin, curing agent) such as colorant, low stress agent, defoaming agent, leveling agent, ultraviolet absorber, foaming agent, antioxidant, flame retardant, ion scavenger, etc. And additives other than inorganic fillers, curing accelerators, and coupling agents). 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 may be, for example, 30% by weight to 80% by weight, and more preferably 40% by weight to 70% by weight. It is good also as follows. 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 this embodiment can be obtained by film-forming the thermosetting resin composition that is in the form of a varnish. 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 this embodiment, you may implement the process of removing a solvent, for example on the conditions of 100 to 150 degreeC and 1 minute-5 minutes. Thereby, it is possible to sufficiently remove the solvent while suppressing the curing of the resin film containing the thermosetting resin.

  In addition, the usage form of the thermosetting resin composition of the present embodiment is not particularly limited, but for example, a resin film made of the thermosetting resin composition, with a carrier provided with the resin film on a carrier substrate. A resin film, 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 curing of the thermosetting resin composition Examples thereof include a resin substrate having an insulating layer made of a material, a printed wiring board having a circuit layer formed on the surface of the metal-clad laminate or the resin substrate.

(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 substrate 12 and a resin film 10 made of the thermosetting resin composition provided on the carrier substrate 12. Can be provided. Thereby, the handleability of the resin film 10 can be improved.

  The carrier-attached resin film 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 and / or a copper-based alloy, aluminum and / or an aluminum-based alloy, iron and / or an iron-based alloy, silver and / or a silver-based alloy, gold and a gold-based alloy, for example. Zinc and zinc-based alloys, nickel and nickel-based alloys, tin and tin-based alloys, and the like. Among these, a sheet made of polyethylene terephthalate is most preferable because it is inexpensive and easy to adjust the peel strength. Thereby, it becomes easy to peel from the resin film with carrier 100 with an appropriate strength.

  The lower limit value of the thickness of the resin film 10 is not particularly limited, but may be, for example, 1 μm or more, 3 μm or more, or 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 may be, for example, 500 μm or less, 300 μm or less, or 100 μm or less. Thereby, the semiconductor device can be thinned.

  Although the thickness of the carrier base material 12 is not specifically limited, For example, 10-100 micrometers may be sufficient and it is good also as 10-70 micrometers. Thereby, the handleability at the time of manufacturing the resin film 100 with a carrier is favorable and preferable.

  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 said resin sheet is a multilayer, it may be comprised by the same kind and may be comprised by different types. 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. For example, the varnish-like thermosetting resin composition is applied onto the carrier substrate 12 using various coater apparatuses. After the coating film is formed by the above method, a method of removing the solvent by appropriately drying the coating film 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 fiber base material with a thermosetting resin composition and then semi-curing it. The sheet-like material having such a structure is excellent in various properties such as dielectric properties, mechanical and electrical connection reliability under high temperature and high humidity, and is suitable for manufacturing an insulating layer of a printed wiring board.

  The method for impregnating the fiber base material with the thermosetting resin composition is not particularly limited. For example, a resin varnish is prepared by dissolving the thermosetting resin composition in a solvent, and the fiber base material is immersed in the resin varnish. A method of applying the resin varnish to the fiber substrate by various coaters, a method of spraying the resin varnish to the fiber substrate by spraying, and laminating both surfaces of the fiber substrate with the resin film made of a thermosetting resin composition. And the like.

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

(Metal-clad laminate)
In this embodiment, the metal-clad laminate has a metal layer disposed on at least one surface of a 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-alloy, invar, super-invar and other Fe—Ni-based alloys, W, Mo, and the like. Among these, the metal constituting the metal foil 105 is preferably copper or a copper alloy because of its excellent conductivity, easy circuit formation by etching, and low cost. That is, the metal foil 105 is preferably a copper foil.
Further, as the metal foil, a metal foil with a carrier or the like can also be used.
The thickness of the metal foil is preferably 0.5 μm or more and 20 μm or less, and more preferably 1.5 μm or more and 18 μm or less.

Subsequently, the fiber base material used for this embodiment is demonstrated.
Although it does not specifically limit as 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, Preferably it is 5 micrometers or more and 150 micrometers or less, More preferably, they are 10 micrometers or more and 100 micrometers or less, More preferably, they are 12 micrometers or more and 90 micrometers or less. By using the fiber base material having such a thickness, the handling property at the time of producing the prepreg can be further improved.
When the thickness of the fiber base material is not more than the above upper limit, the impregnation property of the 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, handling properties can be improved, production of a prepreg can be facilitated, and warping 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 characteristic of the thermosetting resin composition of this embodiment is demonstrated.

  The lower limit of the storage elastic modulus at 30 ° C. of the cured product of the thermosetting resin composition of the present embodiment is, for example, 5 GPa or more, preferably 8 GPa or more, and more preferably 10 GPa or more. Thereby, the hardened | cured material of a high elasticity modulus is realizable. On the other hand, the upper limit value of the storage elastic modulus at 30 ° C. is not particularly limited, but may be, for example, 20 GPa or less.

  Moreover, the lower limit of the storage elastic modulus at 260 ° C. of the cured product of the thermosetting resin composition of the present embodiment is, for example, 1 GPa or more, preferably 1.5 GPa or more, more preferably 2 GPa or more. is there. Thereby, the hardened | cured material of high elasticity modulus is realizable also in a high temperature environment. On the other hand, the upper limit value of the storage elastic modulus at 260 ° C. is not particularly limited, but may be 5 GPa or less, for example, or 4 GPa or less.

In this embodiment, for a cured product of a thermosetting resin composition obtained by heat treatment at 220 ° C. for 2 hours, for example, using a dynamic viscoelasticity measuring device, a frequency of 1 Hz and a heating rate of 5 ° C./min. The storage elastic modulus (E ′ ₃₀ , E ′ ₂₆₀ ) at 30 ° C. and 260 ° C. can be calculated from the measurement results 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.

  Although the lower limit of the glass transition temperature of the cured product of the thermosetting resin composition of the present embodiment is not particularly limited, for example, it is 200 ° C or higher, preferably 220 ° C or higher, more preferably 240 ° C or higher. Yes, and more preferably 250 ° C. or higher. Thereby, the hardened | cured material excellent in heat resistance is obtained. Moreover, heat resistance suitable as an insulating layer in a printed wiring board can be implement | achieved by setting it as 240 degreeC or more. Moreover, although the upper limit of the glass transition temperature of the said hardened | cured material is not specifically limited, For example, it is good also as 400 degrees C or less, and good also as 350 degrees C or less.

  The glass transition temperature can be measured using a dynamic viscoelasticity analyzer (DMA) on a cured product of a thermosetting resin composition obtained by heat treatment at 220 ° C. for 2 hours. The glass transition temperature is a temperature at which the loss tangent tan δ has a maximum value 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.

  The upper limit of the average linear expansion coefficient in the plane direction (XY direction) calculated in the range of 30 ° C. to 250 ° C. of the cured product of the thermosetting resin composition of the present embodiment is, for example, 60 ppm / ° C. or less, Preferably it is 55 ppm / ° C. or less, more preferably 50 ppm / ° C. or less. Thereby, the curvature of a semiconductor package can be reduced. 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 more.

  The average linear expansion coefficient is a temperature range of 30 to 300 ° C. and a rate of temperature increase using a thermomechanical analyzer TMA for a cured product of a thermosetting resin composition obtained by heat treatment at 220 ° C. for 2 hours. The linear expansion coefficient in the plane direction (XY direction) in the range of 30 ° C. to 250 ° C. in the second cycle when two cycles of thermomechanical analysis (TMA) were measured under the conditions of 10 ° C./min, load 10 g, and tensile mode. It can be an average value.

(Printed wiring 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 made of the resin film of the present embodiment may not contain 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.

  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.
For example, the metal layer 303 is formed on the surface of an insulating layer (for example, the insulating layer 301 or the insulating layer 305) made of the metal foil 105 that has been subjected to chemical treatment or plasma treatment or the cured resin film of the present embodiment (for example, the insulating layer 301 or the insulating layer 305). (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 layer 309 by removal and flash etching.

  Moreover, the printed wiring board 300 of this embodiment can be made into the resin substrate which 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. 3A and 3B are cross-sectional views illustrating an example of the configuration of the semiconductor device 400. FIG.
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, but may have various structures. For example, a fan-out structure may be used. The insulating layer made of the cured resin film of this 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. FIG. 4 is a process cross-sectional view of an example of the manufacturing process of the printed wiring board 500. FIG. 4C shows a printed wiring board 500 that does not have a core layer.
The printed wiring board 500 of this embodiment does not include a core layer having a fiber base material, and can be, for example, a coreless resin substrate configured with a buildup layer or a solder resist layer. These build-up layers and solder resist layers are preferably composed of an insulating layer made of 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 made of 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 or electrode pads, and 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 disposed 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 may be formed of an insulating layer made of a cured product of the resin film of the present embodiment. Good. 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. Since the linear expansion coefficient of the cured product of the resin film of this embodiment can be reduced, 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.

  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 via wiring 616 in which a metal film is embedded in the via by a plating method is formed. 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 may be formed of an insulating layer made of a cured product of the resin film of the present embodiment. Good. 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.

  Further, the printed wiring board 700 of this 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 mentioned above, although embodiment of this invention was described with reference to drawings, these are the illustrations of this invention, Various structures other than the above are also employable.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited to description of these Examples at all.

(Preparation of thermosetting resin composition)
About the Example and the comparative example, the varnish-like thermosetting resin composition was prepared.
First, each component was dissolved or dispersed at a solid content ratio shown in Table 1, and 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: phenol aralkyl type epoxy resin having a biphenylene skeleton (Nippon Kayaku Co., Ltd., NC-3000, epoxy equivalent 275, weight average molecular weight 2000)
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: Triphenylmethane type epoxy resin (EPKA-502H manufactured by Nippon Kayaku Co., Ltd., multifunctional / branched solid epoxy resin, epoxy equivalent: 168 g / eq)

(Multifunctional phenolic resin)
Polyfunctional phenol resin 1: Polyfunctional phenol resin having biphenylene skeleton containing aldehyde group and imino group obtained by the following synthesis method [Synthesis method of resin including polyfunctional phenol resin 1]
850 g (6.767 mol) of orthohydroxybenzaldehyde, 421.9 g (1.741 mol) of bismethoxymethylbiphenyl, 8.5 g of paratoluenesulfonic acid (orthohydroxy) in a 1 L internal reaction vessel equipped with a thermometer, stirrer and condenser. 1 wt% with respect to benzaldehyde) was added, the temperature was raised to 160 ° C., and the reaction was carried out for 4 hours. Methanol produced as a by-product in the reaction was removed out of the system. After completion of the reaction, neutralization and washing with water were carried out to remove unreacted orthohydroxybenzaldehyde monomer to obtain an aldehyde-containing biphenyl resin.
100.0 g of the obtained aldehyde-containing biphenyl resin was dissolved in 100.0 g of toluene and heated to 80 ° C. Next, 25.4 g of allylamine was added over 2 hours while paying attention to heat generation. Thereafter, the used toluene was removed at 160 ° C. to obtain a resin containing a polyfunctional phenol resin (polyfunctional phenol resin 1) having an aldehyde group- and imino group-containing biphenylene skeleton.

(Curing agent)
Phenol-based curing agent 1: phenol aralkyl resin having a biphenylene skeleton (Nippon Kayaku Co., Ltd., KAYAHARD GPH-65, OH equivalent: 200 g / eq)
Phenol-based curing agent 2: phenolic resin-based curing agent (multifunctional, manufactured by Nippon Kayaku Co., Ltd., KAYAHARD KTG-105, OH equivalent: 105 g / eq)
(Inorganic filler)
Inorganic filler 1: Silica particles (manufactured by Admatech, SC2050, average particle size 0.5 μm)
(Curing accelerator)
Curing accelerator 1: 2-phenyl-1H-imidazole 4,5-dimethanol (manufactured by Shikoku Kasei Co., Ltd., Curazole 2PHZ-PW)
Curing accelerator 2: 2-phenylimidazole (manufactured by Shikoku Kasei Co., Ltd., Curazole 2PZ-PW)
Curing accelerator 3: 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole (manufactured by Shikoku Kasei Co., Ltd., Curazole TBZ)

(Production of resin film with carrier)
Subsequently, the resin film with a carrier was produced using the thermosetting resin composition. Specifically, a thermosetting resin composition (resin varnish) is applied onto polyethylene terephthalate, and then the solvent is removed by drying at a temperature of 140 ° C. for 2 minutes to produce a resin film with a carrier having a thickness of 25 μm. did.

(Prepreg)
In Examples and Comparative Examples, the resin varnish was impregnated into a glass cloth by applying the obtained resin varnish to a glass cloth (cross type # 1078, E glass, basis weight 48 g / m ² ). Thereafter, it was dried in a heating furnace at 180 ° C. for 2 minutes to obtain a prepreg having a thickness of 70 μm. The resin content (RC) in the thermosetting resin composition in the prepreg of each example and each comparative example was 64% by weight based on the solid content of the entire prepreg (glass cloth and thermosetting resin composition). there were.

  In Examples and Comparative Examples, the following evaluation was performed. The evaluation results are shown in Table 1.

(Hardened resin film)
The obtained resin film with a carrier was laminated and laminated so as to have a thickness of about 100 μm. Thereafter, a copper foil having a thickness of 12 μm was laminated on both surfaces, heat-treated at 220 ° C. for 2 hours, and then subjected to copper etching to obtain a cured resin product of a thermosetting resin composition. Lamination is performed using a two-stage vacuum / pressure laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.) for 30 seconds under a pressure of 10 hPa or less, at a temperature of 80 ° C., a pressure of 0.8 MPa, and a pressure of 30 seconds. And vacuum heating and pressure forming. Two stages were not used.

(Hardened prepreg)
The obtained prepreg was heat-treated at 220 ° C. for 2 hours to obtain a prepreg cured product of a thermosetting resin composition.

(Glass transition temperature, storage modulus at 30 ° C. E _'30, the storage modulus E at 260 ° C.' ₂₆₀₎
An 8 mm × 40 mm test piece was cut out from the obtained cured resin, and a dynamic viscoelasticity measurement (DMA device, manufactured by TA Instrument Co., Ltd., Q800) was used for the test piece. The dynamic viscoelasticity measurement was performed at a frequency of 1 Hz and the storage elastic modulus E ′ _{30 at 30} ° C. and the storage elastic modulus E ′ ₂₆₀ at 260 ° C. were calculated. The glass transition temperature was a temperature at which the loss tangent tan δ showed the maximum value.

(Water absorption rate Wa2 (%))
Five pieces of 6 mm square were cut out from the obtained prepreg cured product to make a sample, and the initial weight A of the sample after being left in a dryer at 85 ° C. for 2 hours was measured, and then in a tank of 85 ° C. and humidity 85% The water absorption rate Wa1 (%) in the cured product was calculated by the following formula by measuring the weight B of the sample after left for 2 hours.
Here, the water absorption rate Wa1 (%) of the sample (cured product) is expressed by the following equation.
Water absorption rate Wa1 [%]: ((BA) / A) × 100
A: Weight after being left in a dryer at 85 ° C. for 2 hours (mg)
B: Weight after being left in a tank at 85 ° C. and 85% humidity for 2 hours (mg)
The water absorption rate Wa2 (%) of the resin in the cured product was obtained by dividing the obtained water absorption rate Wa1 (%) by the resin content (RC: 0.64).

(Linear expansion coefficient (CTE))
A test piece of 4 mm × 20 mm was prepared from the obtained cured resin. About this test piece, thermomechanical analysis was carried out under the conditions of a temperature range of 30 to 300 ° C., a temperature increase rate of 10 ° C./min, a load of 10 g, and a tensile mode using a thermomechanical analyzer TMA (TA Instruments, Q400). (TMA) was measured for two cycles. From this result, the average value of the linear expansion coefficient (CTE) in the plane direction (XY direction) in the range of 30 ° C. to 250 ° C. in the second cycle was calculated. In addition, the value of 2nd cycle was employ | adopted for the linear expansion coefficient.

(Substrate reliability: hygroscopic solder heat resistance test)
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 prepregs obtained in the examples and comparative examples were decompressed for 30 seconds using a two-stage vacuum / pressure laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.) at 10 hPa or less and a temperature of 120 as a one-stage condition. C., pressure 0.8 MPa, 30 seconds, as a two-stage condition, vacuum heating and pressing were performed with a SUS end plate at a temperature of 120.degree. C. and a pressure of 1.0 MPa for 60 seconds. Thereafter, a 12 μm thick copper foil was laminated under the same conditions and then cured at 220 ° C. for 2 hours. An outer layer pattern of the obtained multilayer wiring board was formed, and an evaluation sample having an interlayer thickness of 20 μm was produced.
Using the obtained evaluation sample, the PCT layer was used, and after treatment at 121 ° C., 2 atm for 2 hours, it was infiltrated into the solder layer at 288 ° C. and heat-treated for 30 seconds, and then the presence or absence of blistering was evaluated. This was repeated until swelling occurred, and the number of times until swelling occurred was measured.
○: No swelling even after 11 times (good)
×: Swells once (cannot be used)

It turned out that the thermosetting resin composition of Examples 1-4 can make a glass transition temperature high compared with the comparative example 1 which each contains the epoxy resin which has an epoxy group, and the phenol resin which has a phenolic hydroxyl group. In addition, it turned out that the thermosetting resin composition of Examples 1-4 can reduce the moisture absorption rate in resin compared with the comparative example 2 containing a polyfunctional epoxy resin and a polyfunctional phenol resin. Therefore, it was found that by using the thermosetting resin compositions of Examples 1 to 4, a printed wiring board or a semiconductor device having a structure excellent in substrate reliability can be realized.
Further, since the thermosetting resin compositions of Examples 1 to 4 can reduce the linear expansion coefficient as compared with Comparative Examples 1 and 2, they are excellent in interlayer connection reliability and printed with reduced package warpage. Wiring boards and semiconductor devices can be realized.
In addition, the thermosetting resin compositions of Examples 1 to 4 have a low water absorption rate, a high storage elastic modulus, and a low linear expansion coefficient compared to Comparative Example 3 that does not include an inorganic filler. The substrate reliability was found to be excellent.

  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.

DESCRIPTION OF SYMBOLS 10 Resin film | membrane 12 Carrier base material 100 Resin film | membrane with carrier 105 Metal foil 300 Printed wiring board 301 Insulating layer 303 Metal layer 305 Insulating layer 307 Via hole 308 Electroless metal plating film 309 Electrolytic metal plating layer 400 Semiconductor device 401 Insulating layer 407 Semiconductor element 410 Solder bump 413 Sealing material layer 500 Printed wiring board 510 Support board 520 Carrier foil 530 Metal foil 540 Insulating layer 542 Metal layer 550 Insulating layer 552 Metal layer 560 Insulating layer 562 Metal layer 600 Printed wiring board 610 Coreless resin substrate 612 Insulating layer 614 Metal layer 616 Via wiring 618 Metal layer 620 Semiconductor element 630 Insulating layer 632 Insulating layer 640 Metal layer 650 Metal layer 652 First metal layer 654 Second metal layer 700 Printed wiring board 710 Coreless resin substrate 712 Insulating layer 7 4 metal layer 716 via wiring 718 metal layer 720 semiconductor element 730 insulating layer 732 insulating layer 740 metal layer

Claims (15)

A thermosetting resin composition used for forming an insulating layer in a printed wiring board,
A polyfunctional phenol resin comprising, in one molecule, an aldehyde group and a functional group that reacts with the aldehyde group and is different from the aldehyde group;
An inorganic filler,
Content of the said inorganic filler with respect to 100 weight% of total solid of the said thermosetting resin composition is 50 to 90 weight%, and the average particle diameter of the said inorganic filler is 0.01 to 5.0 micrometer. The thermosetting resin composition which is the following. The thermosetting resin composition according to claim 1,
A thermosetting resin composition, wherein the functional group is an imino group. The thermosetting resin composition according to claim 1 or 2,
The thermosetting resin composition whose storage elastic modulus in 30 degreeC of the hardened | cured material of the said thermosetting resin composition is 5 GPa or more and 20 GPa or less. The thermosetting resin composition according to any one of claims 1 to 3,
The thermosetting resin composition whose glass transition temperature of the hardened | cured material of the said thermosetting resin composition is 200 degreeC or more. The thermosetting resin composition according to any one of claims 1 to 4,
The thermosetting resin composition whose average linear expansion coefficient computed in the range of 30 to 250 degreeC of the hardened | cured material of the said thermosetting resin composition is 1 ppm / degrees C or more and 60 ppm / degrees C or less. The thermosetting resin composition according to any one of claims 1 to 5,
A thermosetting resin composition in which the polyfunctional phenol resin has a biphenyl skeleton. The thermosetting resin composition according to any one of claims 1 to 6,
The thermosetting resin composition in which the polyfunctional phenol resin contains a compound represented by the following general formula.

(In the above general formula, Y and Z each represent an aldehyde group, an imino group, or a hydrogen atom, a and b each represent an integer of 1 to 3, X represents a divalent aromatic group, and n represents X, Z and b contained in each repeating unit may be the same or different, provided that at least one aldehyde group and imino group are present in Y and Z in the repeating unit. Including) The thermosetting resin composition according to any one of claims 1 to 7,
A thermosetting resin composition further comprising a thermosetting resin which is an epoxy resin or a bismaleimide resin. The thermosetting resin composition according to any one of claims 1 to 8,
A thermosetting resin composition, wherein the inorganic filler contains silica. The thermosetting resin composition according to any one of claims 1 to 9,
The thermosetting resin composition whose glass transition temperature of the hardened | cured material of the said thermosetting resin composition is 240 degreeC or more and 400 degrees C or less. A carrier substrate;
The resin film with a carrier provided with the resin film which consists of the thermosetting resin composition of any one of Claim 1 to 10 provided on the said 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 10.   A metal-clad laminate in which a metal layer is disposed on at least one surface of a cured product of the prepreg according to claim 12.   A printed wiring board in which a circuit layer is formed on the surface of the metal-clad laminate according to claim 13. A printed wiring board according to claim 14,
A semiconductor device comprising: a semiconductor element mounted on the circuit layer of the printed wiring board or built in the printed wiring board.

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