JP6720652B2 - Thermosetting resin composition, resin film with carrier, printed wiring board and semiconductor device - Google Patents

Description

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

In the past epoxy resin compositions, various developments have been made from the viewpoint of mechanical properties. An example of this type of technology is the epoxy resin composition described in Patent Document 1. According to the document, a triblock copolymer of poly(methyl methacrylate)/poly(butyl acrylate)/poly(methyl methacrylate) is used from the viewpoint of fracture toughness of a cured product of an epoxy resin composition (Patent Paragraph 0021) of Reference 1. Dicyandiamide or 4,4-diaminodiphenylsulfone is used as a curing agent for this epoxy resin composition (paragraph 0034 of Patent Document 1, Example).

JP, 2005-178630, A

However, in recent years, semiconductor packages have become thinner and thinner. Based on such a development environment, the present inventor studied and found that the cured product of the epoxy resin composition described in the above literature has room for improvement in terms of toughness.

The present inventor further examined the thermosetting resin composition used for forming the insulating layer in the printed wiring board, and focused on the degree of dispersion of the (meth)acrylic block copolymer in the thermosetting resin composition. Came to. Based on such points of view, as a result of intensive studies, the degree of dispersion of the (meth)acrylic block copolymer in the thermosetting resin composition was determined by comparing the (meth)acrylic block copolymer with the curing agent. It was found that evaluation can be performed by using the Hansen solubility parameter distance (HSP distance) as an index.

Based on such findings, the above index was further studied, and as a result, by setting the Hansen solubility parameter distance between the (meth)acrylic block copolymer and the curing agent to a predetermined value or less, the thermosetting resin composition was obtained. It was found that the toughness of the thermosetting product can be improved, and the present invention has been completed.

According to the invention,
A thermosetting resin composition used for forming an insulating layer in a printed wiring board,
A thermosetting resin,
Hardener,
An inorganic filler,
Including a (meth)acrylic block copolymer,
A thermosetting resin composition is provided, wherein the curing agent includes one or more first curing agents having a Hansen solubility parameter distance of 16 MPa ^1/2 or less from the (meth)acrylic block copolymer. ..

According to the invention,
A carrier substrate,
There is provided a resin film with a carrier, comprising: a resin film formed on the carrier substrate, the resin film comprising the thermosetting resin composition.

According to the invention,
There is provided a printed wiring board including an insulating layer made of a cured product of the thermosetting resin composition.

According to the invention,
With the printed wiring board,
A semiconductor device mounted on a circuit layer of the printed wiring board or built in the printed wiring board.

ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition which can obtain the insulating layer excellent in toughness, the resin film with a carrier using the same, a printed wiring board, and a semiconductor device are provided.

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. FIG. 6 is a process cross-sectional view showing an example of the manufacturing process of the printed wiring board in the present 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 constituents will be referred to with the same numerals, and the description thereof will not be repeated.

The thermosetting resin composition of the present embodiment contains a thermosetting resin, a curing agent, an inorganic filler, and a (meth)acrylic block copolymer, and the curing agent is the above (meth). One or more first curing agents having a Hansen solubility parameter distance of 16 MPa ^1/2 or less from the acrylic block copolymer may be included. Such a thermosetting resin composition is used for forming an insulating layer in a printed wiring board.

The present inventor further examined the thermosetting resin composition used for forming the insulating layer in the printed wiring board, and focused on the degree of dispersion of the (meth)acrylic block copolymer in the thermosetting resin composition. Came to.
Based on such points of view, as a result of intensive studies, the degree of dispersion of the (meth)acrylic block copolymer in the thermosetting resin composition was determined by comparing the (meth)acrylic block copolymer with the curing agent. It was found that optimum evaluation is possible by using the Hansen solubility parameter distance (HSP distance) as an index. In addition, this index also applies to a (meth)acrylic block copolymer in a thermosetting resin composition containing a thermosetting resin, a curing agent, an inorganic filler, and a (meth)acrylic block copolymer. It was found that the degree of dispersion of the polymer can be evaluated.
Based on such knowledge, the above index was further studied, and as a result, the Hansen solubility parameter distance between the (meth)acrylic block copolymer and the curing agent was set to 16 MPa ^1/2 or less, whereby the thermosetting resin The inventors have found that the toughness of the thermosetting composition can be improved, and completed the present invention.

According to the present embodiment, the thermosetting property is improved by using the curing agent containing one or more first curing agents having a Hansen solubility parameter distance of 16 MPa ^1/2 or less from the (meth)acrylic block copolymer. The toughness of the cured product of the resin composition can be improved.

Although the mechanism is unknown, by increasing the dispersibility of the (meth)acrylic block copolymer in the thermosetting resin composition, the absorption region of the breaking energy in the cured product of the thermosetting resin composition becomes uniform. It is believed to be present and improve the toughness of the cured product.

Further, according to the present embodiment, by improving the dispersibility of the (meth)acrylic block copolymer, the matrix phase formed by curing the thermosetting resin is added to the (meth)acrylic block copolymer. Since a microphase-separated structure in which the polymer block phase is dispersed can be formed and the domain diameter of the polymer block layer can be reduced, the toughness of the cured product is improved.

Furthermore, according to the present embodiment, by improving the dispersibility of the (meth)acrylic block copolymer, the (meth)acrylic block copolymer bleeds on the surface of the cured product of the thermosetting resin. Can be suppressed. Therefore, the adhesion of the cured product of the resin film can be improved. For example, the adhesion of metal such as copper can be improved. This makes it possible to realize an insulating layer having excellent semi-additive process characteristics (SAP characteristics).

In the present embodiment, the insulating layer in the printed wiring board can be used as an insulating member such as a core layer, a buildup layer (interlayer insulating layer), a solder resist layer, or the like that constitutes the printed wiring board. Examples of the printed wiring board include a core layer, a buildup layer (interlayer insulating layer), a printed wiring board having a solder resist layer, a printed wiring board having no core layer, a coreless substrate used in a panel package process (PLP), and a 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 above-mentioned insulating layer, for example, as a buildup layer, a solder resist layer, or a PLP in a printed wiring board having no core layer. It can also be used as an interlayer insulating layer or a solder resist layer of a coreless substrate, an interlayer insulating layer or a solder resist layer of a MIS substrate, and the like. As described above, the cured product of the resin film according to the present embodiment is used in a large-sized printed wiring board used for collectively manufacturing a plurality of semiconductor packages, and an interlayer insulating layer or a solder resist that composes the printed wiring board. It can also be suitably used for the layer.

Since the cured product of the resin film of the present embodiment is used for the insulating layer, it has excellent toughness. Therefore, during the panel level process for manufacturing a large-area panel size package, the panel (coreless substrate) is warped or is not transported. It is possible to suppress substrate cracks during mounting.

Further, the dispersion state of the (meth)acrylic block copolymer in the cured product of the resin film of the present embodiment can be improved even when the filling amount of the inorganic filler is increased. As a result, the linear expansion coefficient of the cured product of the resin film can be lowered, and thus the warpage of the obtained semiconductor package can be sufficiently suppressed.

Each component of the thermosetting resin composition of this embodiment will be described.

The thermosetting resin composition of the present embodiment contains, for example, a thermosetting resin, a curing agent, an inorganic filler, and a (meth)acrylic block copolymer.

(Thermosetting resin)
Examples of thermosetting resins include epoxy resins, maleimide compounds, and benzoxazine compounds. These may be used alone or in combination of two or more. In this embodiment, the thermosetting resin may contain an epoxy resin.

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-phenylene diisode). Pridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylene diisoprediene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexyl) Bisphenol type epoxy resin such as diene bisphenol type epoxy resin); phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type novolac type epoxy resin, novolac type epoxy resin having condensed ring aromatic hydrocarbon structure Novolac type epoxy resin; biphenyl type epoxy resin; aralkyl type epoxy resin such as xylylene type epoxy resin and biphenylaralkyl type epoxy resin; naphthylene ether type epoxy resin, naphthol type epoxy resin, naphthalenediol type epoxy resin, bifunctional to tetrafunctional Naphthalene type epoxy resin such as naphthalene type epoxy resin, binaphthyl type epoxy resin, naphthalene aralkyl type epoxy resin; anthracene type epoxy resin; phenoxy type epoxy resin; dicyclopentadiene type epoxy resin; norbornene type epoxy resin; adamantane type epoxy resin; fluorene Type epoxy resin and the like.

As the epoxy resin, one of these may be used alone, two or more of them may be used in combination, and one or more of them may be used in combination with their prepolymers.

Among the epoxy resins, from the viewpoint of further improving the heat resistance and insulation reliability of the obtained printed wiring board, bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthalene type epoxy resin, One or more selected from the group consisting of anthracene-type epoxy resin and dicyclopentadiene-type epoxy resin is preferable, and from aralkyl-type epoxy resin, novolac-type epoxy resin having condensed ring aromatic hydrocarbon structure and naphthalene-type epoxy resin. More preferably, 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 Co., Ltd., "EPICLON 830S" manufactured by DIC Co., Ltd. and the like can be used. As the bifunctional naphthalene type epoxy resin, "HP4032", "HP4032D", "HP4032SS" and the like manufactured by DIC can be used. As the tetrafunctional naphthalene type epoxy resin, "HP4700" and "HP4710" manufactured by DIC Corporation 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. ,” “ESN-480” and the like can be used. As the biphenyl type epoxy resin, "YX4000", "YX4000H", "YX4000HK", "YL6121" and the like manufactured by Mitsubishi Chemical Corporation can be used. As the anthracene-type epoxy resin, "YX8800" manufactured by Mitsubishi Chemical Corporation or the like can be used. As the naphthylene ether type epoxy resin, "HP6000", "EXA-7310", "EXA-7331", "EXA-7311L", "EXA7311-G3" and the like manufactured by DIC can be used.

Among these epoxy resins, aralkyl type epoxy resin is particularly preferable. This makes it possible to further improve the moisture absorption solder heat resistance and flame retardancy of the cured product of the resin film.

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

（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 general formula (1), A and B represent an aromatic ring such as a benzene ring and a biphenyl structure. Further, hydrogen in the aromatic ring of A and B may be substituted. Examples thereof include a methyl group, an ethyl group, a propyl group, a phenyl group, etc. n represents a repeating unit and is, for example, an integer of 1 to 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 the formula (1a), n represents an integer of 1 to 5.)

（式（１ｂ）中、ｎは、１〜５の整数を示す。）

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

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

The novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure is naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, triphenylene, tetraphene, or any other novolac type epoxy resin having a 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. Further, it has a high glass transition temperature and thus has excellent heat resistance. Furthermore, since the molecular weight of the repeating structure is large, it is superior in flame retardancy to conventional novolac type epoxy resins.

The novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure is an epoxidized 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 2,3,5trimethylphenol; ethyl such as o-ethylphenol, m-ethylphenol, p-ethylphenol Phenols; alkylphenols such as isopropylphenol, butylphenol, t-butylphenol; phenylphenols such as o-phenylphenol, m-phenylphenol, p-phenylphenol; 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, Examples thereof include naphthalene diols such as 2,7-dihydroxynaphthalene; polyhydric phenols such as resorcin, catechol, hydroquinone, pyrogallol and fluoroglucine; and alkyl polyhydric phenols such as alkylresorcin, alkylcatechol and alkylhydroquinone. Of these, phenol is preferable in terms of cost and 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 thereof include benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, dihydroxybenzaldehyde, trihydroxybenzaldehyde, and 4-hydroxy-3-methoxyaldehyde paraformaldehyde.

The condensed ring aromatic hydrocarbon compound is not particularly limited, and examples thereof include naphthalene derivatives such as methoxynaphthalene and butoxynaphthalene; anthracene derivatives such as methoxyanthracene; phenanthrene derivatives such as methoxyphenanthrene; other tetracene derivatives; chrysene derivatives; pyrene derivatives; Triphenylene derivatives; tetraphene derivatives and the like.

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

(In the above general formula (V), Ar is a condensed ring aromatic hydrocarbon group, R may be the same or different, and a hydrogen atom; a hydrocarbon group having 1 to 10 carbon atoms; halogen; Element; a group selected from an aryl group such as a phenyl group and a benzyl group; and an organic group containing a glycidyl ether, wherein n, p, and q are integers of 1 or more, and the values of p and q are per 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), which may be the same or different, are a hydrogen atom; a hydrocarbon group having 1 to 10 carbon atoms; a halogen element; an aryl group such as a phenyl group and 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 resin such as naphthol type epoxy resin, naphthalene diol type epoxy resin, bifunctional or tetrafunctional naphthalene type epoxy resin and naphthylene ether type epoxy resin are preferable. Thereby, the heat resistance and low thermal expansion of the obtained printed wiring board can be further improved. Here, the naphthalene type epoxy resin is a resin having a naphthalene ring skeleton and having two or more glycidyl groups.
Further, since the naphthalene ring has a higher π-π stacking effect than the benzene ring, the naphthalene-type epoxy resin is particularly excellent in low thermal expansion and low thermal contraction. Furthermore, 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. The naphthol type epoxy resin is, for example, the following general formula (VII-1), the naphthalene diol type epoxy resin is the following formula (VII-2), and the bifunctional or tetrafunctional naphthalene type epoxy resin is the following formula (VII-3). Examples of (VII-4) (VII-5) and the naphthylene ether type epoxy resin can be represented by the following general formula (VII-6).

（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 a number of 1 to 6 on average, and R represents a glycidyl group or a hydrocarbon group of 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。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² 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 one of o and m is 1 or more.)

The lower limit of the weight average molecular weight (Mw) of the epoxy resin is not particularly limited, but may be Mw300 or more, and preferably Mw800 or more. When Mw is at least the above lower limit, it is possible to suppress the tackiness of the cured product of the resin film. The upper limit 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 the resin film is easily formed. 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, and 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 at least the lower limit value described above, the handling property is improved and the resin film is easily formed. 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, for example, 60% by weight or less is preferable, and 45% by weight or less is preferable. It is more preferably 30% by weight or less. When the content of the epoxy resin is less than or equal to the above upper limit, the strength and flame retardancy of the obtained printed wiring board may be improved, or the linear expansion coefficient of the printed wiring board may be reduced, and the effect of reducing warpage may be improved. There are cases.
The total solid content of the thermosetting resin composition refers to the entire components excluding the solvent contained in the thermosetting resin composition. The same applies hereinafter in this specification.

((Meth)acrylic block copolymer)
The thermosetting resin composition of this embodiment may include a (meth)acrylic block copolymer. According to the present embodiment, by sufficiently dispersing the (meth)acrylic block copolymer, the toughness of the obtained insulating layer is increased and the adhesion with other members such as the circuit layer is further improved. You can

The (meth)acrylic block copolymer is, for example, a block copolymer containing a (meth)acrylic monomer as an essential monomer component.
Examples of the (meth)acrylic monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylate. (Meth)acrylic acid alkyl ester such as butyl, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate; (meth)acrylic acid having an alicyclic structure such as cyclohexyl acrylate and cyclohexyl methacrylate Ester; (meth)acrylic acid ester having an aromatic ring such as benzyl methacrylate; (fluoro)alkyl ester of (meth)acrylic acid such as 2-trifluoroethyl methacrylate; acrylic acid, methacrylic acid, maleic acid, maleic anhydride Carboxyl group-containing acrylic monomer having a carboxyl group in the molecule such as acid; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-methacrylic acid 2- Hydroxypropyl, 4-hydroxybutyl methacrylate, mono(meth)acrylic acid ester of glycerin and the like, a hydroxyl group-containing acrylic monomer having a hydroxyl group in the molecule; glycidyl methacrylate, methylglycidyl methacrylate, 3,4-epoxycyclohexylmethyl Acrylic monomer having an epoxy group in the molecule such as methacrylate; Allyl group-containing acrylic monomer having an allyl group in the molecule such as allyl acrylate and allyl methacrylate; γ-methacryloyloxypropyltrimethoxysilane, γ- Silane group-containing acrylic monomer having a hydrolyzable silyl group in the molecule such as methacryloyloxypropyltriethoxysilane; benzo such as 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole Examples thereof include a UV-absorbing acrylic monomer having a triazole-based UV-absorbing group. These may be used alone or in combination of two or more.

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

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

Among these, as the (meth)acrylic block copolymer, a polymer block (S) (soft block) having a low glass transition temperature (Tg) from the viewpoint of improving heat resistance, light resistance, and crack resistance. And a polymer block (H) (hard block) having a Tg higher than that of the polymer block (S), a diblock copolymer having an HS structure, a polymer block (S) and a polymer block (S). H) and a copolymer having alternating polymer blocks, a triblock copolymer having an H-S-H structure having a polymer block (S) in the middle and polymer blocks (H) at both ends thereof are preferable. .. These may be used alone or in combination of two or more.

The Tg of the polymer constituting the polymer block (S) of the (meth)acrylic block copolymer is not particularly limited, but is preferably lower than 30°C. Further, the Tg of the polymer constituting the polymer block (H) is not particularly limited, but is preferably 30° C. or higher. When the (meth)acrylic block copolymer has a plurality of polymer blocks (H), the respective polymer blocks (H) may have the same composition or may have different compositions. Similarly, when the (meth)acrylic block copolymer has a plurality of polymer blocks (S), the respective polymer blocks (S) may have the same composition or different ones. Good.

The monomer component constituting the polymer block (H) is not particularly limited, but examples thereof include a monomer having a homopolymer Tg of 30° C. or higher. Examples of such a monomer include methyl methacrylate, styrene, acrylamide, acrylonitrile and the like.
The monomer component constituting the polymer block (S) is not particularly limited, and examples thereof include a monomer having a homopolymer Tg of less than 30°C. Examples of such a monomer include butyl acrylate, acrylic acid C _2-10 alkyl ester such as 2-ethylhexyl acrylate, and butadiene (1,4-butadiene).

As a preferable specific example of the (meth)acrylic block copolymer, for example, the polymer block (S) is a polymer composed of butyl acrylate (BA) as a main monomer, and the polymer block (H) is Is a polymer composed mainly of methyl methacrylate (MMA), polymethylmethacrylate-block-polybutylacrylate-block-polymethylmethacrylate terpolymer (PMMA-b-PBA-b-PMMA), PMMA-b. -PBA etc. are mentioned.
The above-mentioned PMMA-b-PBA-b-PMMA and PMMA-b-PBA are preferable from the viewpoint of improving heat resistance, light resistance, and crack resistance. The above PMMA-b-PBA-b-PMMA and PMMA-b-PBA are hydrophilic groups (for example, a hydroxyl group, a carboxyl group, a hydroxyl group, a carboxyl group, and the like, if necessary, for the purpose of improving the compatibility with a thermosetting resin or the like. A monomer having an amino group), for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylic acid, etc., is copolymerized with a PMMA block and/or a PBA block. Good.

The number average molecular weight (Mn) of the (meth)acrylic block copolymer is not particularly limited, but is preferably 3,000 or more and 500,000 or less, more preferably 5,000 or more and 100,000 or less. When the number average molecular weight (Mn) is at least the above lower limit, the toughness of the obtained cured product can be made better, and as a result, crack resistance can be further improved. On the other hand, when the number average molecular weight (Mn) is not more than the above upper limit, the compatibility with the thermosetting resin can be improved.

The (meth)acrylic block copolymer can be produced by a known or commonly used method for producing a block copolymer.
Examples of the (meth)acrylic block copolymer include, for example, trade names “Nano Strength M52N”, “Nano Strength M22N”, “Nano Strength M51”, “Nano Strength M52”, “Nano Strength M52N”, “Nano Strength”. Strength M53", "Nano Strength M22" (Arkema, PMMA-b-PBA-b-PMMA), trade name "Nano Strength D51N" (Arkema, PMMA-b-PBA), trade name "Nano Strength E21". It is also possible to use commercially available products such as “Nano Strength E41” (PSt (polystyrene)-b-PBA-b-PMMA, manufactured by Arkema).

In the present embodiment, the lower limit of the content of the (meth)acrylic block copolymer 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. In that case, it may be 0.1% by weight or more, or 1.0% by weight or more. This makes it possible to enhance the toughness of the obtained insulating layer and further improve the adhesion to other members such as the circuit layer. The upper limit of the content of the (meth)acrylic block copolymer is not particularly limited, but when the total solid content of the thermosetting resin composition (that is, the components excluding the solvent) is 100% by weight. 25.0% by weight or less, or 15.0% by weight or less. This can improve the balance between the dispersibility of the (meth)acrylic block copolymer and the mechanical properties of the cured product of the resin film.

(Curing agent)
The thermosetting resin composition of this embodiment may include a curing agent.
The curing agent according to the present embodiment may include at least one first curing agent having a Hansen solubility parameter distance (HSP distance) from the (meth)acrylic block copolymer of 16 MPa ^1/2 or less. preferable.

The Hansen solubility parameter (HSP) is a measure of the solubility of a substance in another substance. HSP represents solubility as a three-dimensional vector. This three-dimensional vector can be typically represented by a dispersion term (δ _d ), a polar term (δ _p ), and a hydrogen bond term (δ _h ). Then, it is possible to determine that those having similar vectors have high solubility. It is possible to determine the degree of vector similarity by the distance (HSP distance) of the Hansen solubility parameter.

Here, the computer software HSPiP developed by Hansen and Abbott includes a function for calculating the HSP distance and a database in which Hansen parameters of various resins and solvents or non-solvents are described. Then, the Hansen solubility parameter (HSP value) used in the present specification can be calculated using software called HSPiP (Hansen Reliability Parameters in Practice). For example, reference may be made to the values described in Solvent list and Polymer list contained in HSPiP 3rd version corrected to 25°C. Here, the resin and solvent or non-solvent not described in the Solvent list can be calculated by an estimation method using a neural network method called Y-MB. By inputting the molecular structure into the Y-MB calculation software attached to HSPiP, it is automatically decomposed into atomic groups, and the HSP value and molecular volume are calculated.

The HSP distance is represented by R ² shown in the following formula (1).
In the present embodiment, the HSP distance is, for example, when the HSP of the (meth)acrylic block copolymer is (d1, p1, h1) and the HSP of the first curing agent is (d2, p2, h2), It can be calculated by the following formula (1).

In the present embodiment, the upper limit of the HSP distance is, for example, ^{16 MPa 1/2} or less, preferably ^{12 MPa 1/2} or less, more preferably ^{10 MPa 1/2} or less. Thereby, the dispersibility of the (meth)acrylic block copolymer can be improved. On the other hand, the lower limit of the HSP distance is not particularly limited, but may be 1 MPa ^1/2 or more, for example.

In the first curing agent of the present embodiment, the upper limit of the polarity term (P) of the HSP is not particularly limited, for example, at ^{10 MPa 1/2} or less, preferably not more ^{8 MPa 1/2} or less, more preferably It is 5 MPa ^1/2 or less. By reducing the distance of the polar term (P) between the first curing agent and the (meth)acrylic block copolymer, the domain diameter of the polymer block phase of the (meth)acrylic block copolymer is reduced. You can Further, the dispersibility of the (meth)acrylic block copolymer can be enhanced even in the thermosetting resin composition highly filled with the inorganic filler. On the other hand, the lower limit of the polar term (P) of HSP is not particularly limited, but may be, for example, 1 MPa ^1/2 or more.

In the first curing agent of the present embodiment, the upper limit of the HSP hydrogen section (H) is not particularly limited, for example, at ^{11 MPa 1/2} or less, preferably not more ^{10 MPa 1/2} or less, more preferably It is 8 MPa ^1/2 or less. Thereby, the dispersed state of the (meth)acrylic block copolymer can be stabilized. The lower limit value of the hydrogen term (H) of HSP is not particularly limited, but may be, for example, 1 MPa ^1/2 or more.

Further, in the first curing agent of the present embodiment, the upper limit of the polar term (P) of HSP is 10 MPa ^1/2 or less, and the upper limit of the hydrogen term (H) of HSP is 11 MPa ^1/2 or less. It is preferable to have. Thereby, the dispersibility of the (meth)acrylic block copolymer can be sufficiently improved. Although the mechanism is unknown, it is considered that the contact between the first curing agent and the (meth)acrylic block copolymer lowers the free energy and stabilizes the dispersed state.

In the first curing agent of the present embodiment, the upper limit of the dispersion term (D) of the HSP is not particularly limited, for example, may be ^{22 MPa 1/2} or less may be ^{21 MPa 1/2} or less, 20 MPa ^It may be ^½ or less. The lower limit of the dispersion term (D) of HSP is not particularly limited, but may be 1 MPa ^1/2 or more, for example.

Further, an amine curing agent having an amino group may be used as the first curing agent. As the amine curing agent, for example, an amine curing agent having a diphenylmethane skeleton may be used.
Moreover, you may use the hardening|curing agent which has a hydroxyl group as a 1st hardening|curing agent. As the curing agent having a hydroxyl group, for example, a phenol-based curing agent may be used, and specifically, a phenol-based curing agent having a novolac skeleton may be used. Thereby, chemical resistance can be improved.

In the present embodiment, the upper limit of the distance (HSP distance) of the Hansen solubility parameter of the amine curing agent, which is the first curing agent, with the (meth)acrylic block copolymer is, for example, 15 MPa ^1/2 or less. At best, it may be ^{12 MPa 1/2} or less may be ^{10 MPa 1/2} or less, may be ^{8 MPa 1/2} or less.
Further, in the present embodiment, the upper limit of the distance (HSP distance) of the Hansen solubility parameter of the curing agent having a hydroxyl group, which is the first curing agent, with the (meth)acrylic block copolymer is, for example, 16 MPa. may be a ^half or less, it may be ^{14 MPa 1/2} or less may be ^{12 MPa 1/2} or less may be ^{10 MPa 1/2} or less. Thereby, the dispersibility of the (meth)acrylic block copolymer can be improved.

Further, as the curing agent of the present embodiment, in addition to the first curing agent, another second curing agent whose HSP distance is not particularly limited may be used together. The second curing agent is not particularly limited, and examples thereof include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2 -Ethyl-4-methylimidazole (EMI24), 2-phenyl-4-methylimidazole (2P4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-methyl-5-hydroxyimidazole (2P4MHZ), 1-benzyl An imidazole compound such as -2-phenylimidazole (1B2PZ); a catalyst type curing agent such as a Lewis acid such as a BF ₃ complex.
Also, for example, aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), m-phenylenediamine, p-phenylenediamine, o-xylenediamine, 4,4′- Diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 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 , Polyamine compounds containing aromatic polyamines such as 3'-diethyl-5,5'-dimethyldiphenylmethane and 3,3'-diethyl-4,4'-diaminodiphenylmethane, as well as dicyandiamide (DICY) and organic acid dihydralazide; Alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA), etc. Acid anhydrides including aromatic acid anhydrides; polymercaptan compounds such as polysulfides, thioesters and thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; polyaddition type compounds such as organic acids such as polyester resins containing carboxylic acid Curing agent: 2,2'-methylenebis(4-ethyl-6-tert-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-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)trione and other phenolic compounds Compounds can also be used.
Further, examples of the second curing agent include phenol resin type curing agents such as novolac type phenol resin and resol type phenol resin; urea resin such as methylol group-containing urea resin; melamine resin such as methylol group-containing melamine resin. Condensation type curing agents may also be used. These may be used alone or in combination of two or more.

The above-mentioned phenol resin-based curing agent is a general monomer, oligomer or polymer having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited, but examples thereof include phenol novolac resin and cresol. Novolac type phenolic resins such as novolac resins and naphthol novolac resins; polyfunctional phenolic resins such as triphenolmethane type phenolic resins; modified phenolic resins such as terpene modified phenolic resins and dicyclopentadiene modified phenolic resins; phenylene skeleton and/or biphenylene Examples thereof include aralkyl type resins such as a phenol aralkyl resin having a skeleton, phenylene and/or naphthol aralkyl resin having a biphenylene skeleton; and bisphenol compounds such as bisphenol A and bisphenol F. These may be used alone or in combination of two or more. Among these, those having a hydroxyl group equivalent 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 4×10 ^{2 to} 1.8×10 ³ , and preferably 5×10 ^{2 to} 1.5×10 ³ . By setting the weight average molecular weight to the above lower limit or more, problems such as tackiness in the prepreg hardly occur, and by setting the weight average molecular weight to the above upper limit or less, the impregnating property to the fiber base material is improved during the preparation of the prepreg, 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, for example, preferably 0.01% by weight or more, and 0.05% by weight or more. More preferably, it is more preferably 0.2% by weight or more. By setting the content of the curing agent to be the above lower limit or more, the effect of promoting curing can be sufficiently exhibited. On the other hand, the upper limit of the content of the curing agent is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, but is, for example, preferably 25% by weight or less, more preferably 20% by weight or less. 15% by weight or less is more preferable. When the content of the curing agent is at most the above upper limit value, the storage stability of the prepreg can be further improved.

The lower limit of the content of the first 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 and 0.05% by weight, for example. % Or more is more preferable, and 0.2% by weight or more is further preferable. Thereby, the dispersibility of the (meth)acrylic block copolymer can be sufficiently improved. On the other hand, the upper limit of the content of the first 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 25% by weight or less, and 20% by weight or less, for example. It is more preferably 15% by weight or less. Thereby, the balance with the other second curing agent can be improved.

(Inorganic filler)
The thermosetting resin composition of this embodiment may include an inorganic filler.
Examples of the inorganic filler include talc, calcined clay, uncalcined clay, mica, silicates such as glass; oxides such as titanium oxide, alumina, boehmite, silica, fused silica; calcium carbonate, magnesium carbonate, hydro Carbonates such as talcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, 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 kind among these may be used alone, or two or more kinds may be used in combination.

The lower limit of the average particle size of the inorganic filler is not particularly limited, but may be, for example, 0.01 μm or more, or 0.05 μm or more. As a result, the viscosity of the varnish of the thermosetting resin can be suppressed from increasing, and the workability at the time of producing the insulating layer can be improved. The upper limit of the average particle size of the inorganic filler is not particularly limited, but is, for example, preferably 5.0 μm or less, more preferably 2.0 μm or less, still more preferably 1.0 μm or less. This makes it possible to suppress a phenomenon such as sedimentation of the inorganic filler in the varnish of the thermosetting resin, and to obtain a more uniform resin film. Further, 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 diameter of the inorganic filler is, for example, a laser diffraction type particle size distribution measuring device (LA-500 manufactured by HORIBA, Inc.), the particle size distribution of the particles is measured on a volume basis, and the median diameter (D50 thereof). ) Can be used as the average particle size.

The inorganic filler is not particularly limited, but an inorganic filler having an average particle diameter of monodisperse or an inorganic filler having an average particle diameter of polydisperse may be used. Further, one kind or two or more kinds of inorganic fillers having an average particle diameter of monodisperse and/or polydisperse 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, and 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. In addition, the warp 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 90% by weight or less and 85% by weight or less, for example. Or 80% by weight or less. Thereby, the processability of the cured product of the resin film can be improved.

(Cyanate resin)
The thermosetting resin composition of this embodiment may 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, but can be obtained, for example, by reacting a cyanogen halide compound with phenols or naphthols and, if necessary, prepolymerizing by a method such as heating. Further, a commercial product prepared in this manner can also be used.
By using the cyanate resin, the linear expansion coefficient of the cured product of the resin film can be reduced. Furthermore, the electrical properties (low dielectric constant, low dielectric loss tangent), mechanical strength, etc. of the cured product of the resin film can be improved.

Examples of the cyanate resin include novolac type cyanate resin; bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethylbisphenol F type cyanate resin, and other bisphenol type cyanate resins; reaction of naphthol aralkyl type phenol resin with cyanogen halide. Examples thereof include the naphthol aralkyl type cyanate resin, the dicyclopentadiene type cyanate resin and the biphenylalkyl type cyanate resin obtained in the above. Among these, novolac type cyanate resins and naphthol aralkyl type cyanate resins are preferable, and novolac type cyanate resins are more preferable. By using the novolac type cyanate resin, the crosslink density of the cured product of the resin film is increased and the heat resistance is improved.

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

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

The average repeating unit n of the novolac 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, more preferably 2 or more. When the average repeating unit n is at least the above lower limit value, the heat resistance of the novolac type cyanate resin is improved, and the low molecular weight substance can be prevented from desorbing and volatilizing during heating. The average repeating unit n is not particularly limited, but is preferably 10 or less, more preferably 7 or less. When n is not more than the above upper limit value, the melt viscosity can be suppressed from increasing and the moldability of the resin film can be improved.

Further, 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 a reaction with di(2-hydroxy-2-propyl)benzene or the like and a 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 is less likely to occur during synthesis, liquid separation during washing with water is improved, and a decrease in yield tends to be prevented.

（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.)

The cyanate resin may be used alone or in combination of two or more kinds, or may be used in combination of one kind or two or more kinds with those prepolymers.

The lower limit of the cyanate resin content is, for example, preferably 1% by weight or more, more preferably 2% by weight or more, further preferably 3% by weight or more, based on 100% by weight of the total solid content of the thermosetting resin composition. preferable. It is possible to achieve a low linear expansion and a high elastic modulus of the cured product of the 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, more preferably 25% by weight or less. 20% by weight or less is more preferable. It is possible to improve heat resistance and moisture resistance. 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 the present embodiment may include, for example, a curing accelerator. Thereby, the curability of the thermosetting resin composition can be improved. As the curing accelerator, one that accelerates the curing reaction of the thermosetting resin can be used, and the type thereof is not particularly limited. In the present embodiment, as the curing accelerator, for example, zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, zinc octylate, bisacetylacetonato cobalt (II), trisacetylacetonato cobalt (III). Such as organic metal salts, triethylamine, tributylamine, tertiary amines such as diazabicyclo[2,2,2]octane, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, Imidazoles such as 2-phenyl-4-ethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxyimidazole , Phenol, bisphenol A, nonylphenol, and other phenol compounds, acetic acid, benzoic acid, salicylic acid, paratoluenesulfonic acid, and other organic acids, and one or more selected from onium salt compounds. Among these, it is more preferable to include an onium salt compound from the viewpoint of more effectively improving the curability.

The onium salt compound used as the curing accelerator is not particularly limited, but for example, a compound represented by the 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 heterocycle, or a substituted or unsubstituted A- represents an aliphatic group, which may be the same or different from each other A ^- is an anion of an n (n≧1)-valent proton donor having at least one proton that can be released outside the molecule. , Or its complex anion)

The lower limit of the content of the curing accelerator may be, for example, 0.01% by weight or more, and preferably 0.05% by weight or more, based on 100% by weight of the total solid content of the thermosetting resin composition. May be By setting the content of the curing accelerator to the above lower limit value or more, the curability of the thermosetting resin composition can be more effectively improved. On the other hand, the upper limit of the content of the curing accelerator may be 2.5% by weight or less, and preferably 1% by weight or less, based on 100% by weight of the total solid content of the thermosetting resin composition. Good. By setting the content of the curing accelerator at the upper limit value or less, the storage stability of the thermosetting resin composition can be improved.

(Coupling agent)
The thermosetting resin composition of this embodiment may include a coupling agent. The coupling agent may be added directly when the thermosetting resin composition is prepared, or may be added in advance to the inorganic filler. The use of the 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 product of the resin film can be improved. Further, by using the coupling agent, the adhesiveness with the copper foil can be improved. Further, 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 epoxy silane coupling agents, cationic silane coupling agents, silane coupling agents such as aminosilane coupling agents, titanate coupling agents and silicone oil type coupling agents. One type of coupling agent may be used alone, or two or more types may be used in combination. In this embodiment, the coupling agent may contain a silane coupling agent.
Thereby, the wettability of the interface between the inorganic filler and each resin can be increased, and the heat resistance of the cured product of the resin film can be further improved.

Various kinds of silane coupling agents can be used, and examples thereof include epoxysilane, aminosilane, alkylsilane, ureidosilane, mercaptosilane, and vinylsilane.

Specific compounds include, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, 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. Among these, it is possible to use one kind or a combination of two or more kinds.Of these, epoxysilane, mercaptosilane and aminosilane are preferable, and as the aminosilane, primary aminosilane or anilinosilane is more preferable.

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 coupling agent may be, for example, 0.01% by weight or more, preferably 0.05% by weight, based on 100% by weight of the total solid content of the thermosetting resin composition. The above may be applied. When the content of the coupling agent is at least the above lower limit value, the inorganic filler can be sufficiently coated, 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, based on 100% by weight of the total solid content of the thermosetting resin composition. Good. When the content of the coupling agent is equal to or less than the above upper limit, it is possible to suppress the influence on the reaction, and it is possible to suppress the decrease in bending strength of the cured product of the resin film.

(Additive)
Incidentally, the thermosetting resin composition of the present embodiment, from the group consisting of dyes such as green, red, blue, yellow, and black, pigments such as black pigment, and dyes, within a range that does not impair the object of the present invention. The above-mentioned components (thermosetting resin, curing agent, etc.) including a coloring agent, a low stress agent, a defoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, an ion scavenger, etc. , Inorganic filler, curing accelerator, coupling agent). These may be used alone or in combination of two or more.

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

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

In the present embodiment, the varnish-like thermosetting resin composition may 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, dimethylsulfoxide, 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 in the form of varnish, the solid content of the thermosetting resin composition may be, for example, 30% by weight or more and 80% by weight or less, more preferably 40% by weight or more and 70% by weight or less. It may be as follows. As a result, a thermosetting resin composition having excellent workability and film forming property can be obtained.

The varnish-like thermosetting resin composition contains the above-mentioned 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 revolution type dispersion method. It can be prepared by dissolving, mixing and stirring in a solvent using various mixers described in 1.

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

The resin film of the present embodiment can be obtained by forming a film of the thermosetting resin composition in the form of varnish. For example, the resin film of the present embodiment can be obtained by removing the solvent from the coating film obtained by coating the 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, the step of removing the solvent may be carried out, for example, under conditions of 100° C. to 150° C. and 1 minute to 5 minutes. This makes it possible to sufficiently remove the solvent while suppressing the progress of curing of the resin film containing the thermosetting resin.

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

The resin film with carrier 100 may be in the form of a roll that can be wound up, or in the form of a sheet such as a rectangle.

In the present embodiment, as the carrier base material 12, for example, a polymer film or a metal foil can be used. The polymer film is not particularly limited, for example, polyolefin such as polyethylene and polypropylene, polyester such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, release paper such as silicone sheet, fluorine resin, heat resistance of polyimide resin and the like. And a thermoplastic resin sheet having The metal foil is not particularly limited, but is, for example, copper and/or a copper alloy, aluminum and/or an aluminum alloy, iron and/or an iron alloy, silver and/or a silver alloy, gold and a gold alloy. , 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 the peel strength is easily adjusted. This facilitates peeling from the resin film with carrier 100 with appropriate strength.

The lower limit 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 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. As a result, the semiconductor device can be thinned.

The thickness of the carrier substrate 12 is not particularly limited, but may be, for example, 10 to 100 μm or 10 to 70 μm. This is preferable because it is easy to handle when the resin film with carrier 100 is manufactured.

The resin film with a carrier 100 according to the present embodiment may be a single layer or a multilayer, and may include one kind or two or more kinds of resin films 10. When the resin sheets are multi-layered, they may be composed of the same kind or different kinds. Further, 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 of forming the resin film with carrier 100 is not particularly limited, but for example, a varnish-shaped thermosetting resin composition is applied onto the carrier substrate 12 using various coater devices. After the coating film is formed by, the method of removing the solvent by appropriately drying the coating film can be used.

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

The resin film of the present embodiment is a resin film made of the thermosetting resin composition as described above.
In the present embodiment, in the cured product of the resin film, a micro phase separation structure in which a polymer block phase of a (meth)acrylic block copolymer is dispersed in a matrix phase formed by curing a thermosetting resin It is preferably formed. Thereby, the toughness of the cured product of the resin film can be improved.

In the present embodiment, the shape of the polymer block phase in the micro phase separation structure is preferably spherical, for example. Thereby, the dispersibility of the (meth)acrylic block copolymer in the cured product of the resin film containing the inorganic filler can be improved.

In this case, the upper limit of the domain diameter of the polymer block phase is not particularly limited, but is, for example, 200 nm or less, preferably 150 nm or less, and more preferably 100 nm or less. Thereby, since a uniform dispersion state can be maintained from the formation of the resin film to the curing process, it is possible to prevent the (meth)acrylic block copolymer from bleeding on the surface of the cured product of the resin film. Further, the toughness of the cured product of the resin film can be sufficiently enhanced. On the other hand, the lower limit of the domain diameter is not particularly limited, but may be 10 nm or more, for example.

In the present embodiment, the lower limit of the maximum value of the bending strength in the cured product of the resin film (cured product of the thermosetting resin composition) measured by the three-point bending test is, for example, 30 MPa or more, and preferably 50 MPa. It is above, and more preferably 70 MPa or more. Thereby, the fracture strength of the cured product of the resin film can be increased. Moreover, the upper limit of the maximum value of the bending strength is not particularly limited, but may be, for example, 1000 MPa or less, 900 MPa or less, or 800 MPa or less.

In the present embodiment, the upper limit value of the storage elastic modulus E′ ₂₅ at 25° C. of the cured product of the resin film (cured product of the thermosetting resin composition) measured by the three-point bending test is not particularly limited, For example, it is 20 GPa or less, preferably 18 GPa or less, and more preferably 16 GPa or less. As a result, a cured product of a resin film having excellent low elasticity can be realized. The lower limit value of the storage elastic modulus E′ ₂₅ is not particularly limited, but may be 1 GPa or more, for example.

In the present embodiment, the lower limit value of the bending elongation at 25° C. of the cured product of the resin film (cured product of the thermosetting resin composition) measured by the three-point bending test is not particularly limited, but for example, 1 0.1% or more, preferably 1.5% or more, more preferably 2% or more, still more preferably 3% or more. This makes it possible to provide a cured product of a resin film having excellent extensibility. The upper limit of the bending elongation is not particularly limited, but may be 15% or less, for example.
In this embodiment, since the bending strength and the bending elongation rate can be increased, a cured product of a resin film having excellent toughness can be obtained.

The three-point bending test of the present embodiment can be performed by placing a test piece on two fulcrums arranged at a constant distance and applying a load to one point in the center between the fulcrums. As an example, the cured product of the thermosetting resin composition is obtained by heating the varnish of the thermosetting resin composition at 100° C. for 1 hour and then at 200° C. for 2 hours. The cured product is cut into a test piece having a length of 50 mm and a width of 10 mm. Then, in the three-point bending test, for example, using a precision universal testing machine (manufactured by Shimadzu Corporation, Autograph AG-IS), the distance L between two fulcrums is 5 mm, the thickness of the test piece is 0.1 mm, and the measurement temperature is : 25° C., test speed: 1 mm/min is used. Here, in the above-mentioned three-point bending test, the maximum value of the bending strength is the value of the stress when the bending load becomes maximum under the above conditions, and the storage elastic modulus E′ is from the test force of 0.5 N to 1. The bending elongation is determined by the amount of change in bending load in the range of 0 N, and the bending elongation is determined by the following equation.
Bending elongation: (Equation) 600 x (deflection amount until displacement of test piece (displacement)) x (test piece thickness) / (distance between fulcrums) ²

In the present embodiment, the lower limit of 90° peel strength of the cured product of the resin film (cured product of the thermosetting resin composition) with respect to the copper foil is not particularly limited, but is, for example, 0.5 kN/m or more. And preferably 0.6 kN/m or more, and more preferably 0.7 kN/m or more. Thereby, the copper adhesion of the cured product of the resin film can be improved, and the SAP characteristics of the obtained insulating layer can be improved. The upper limit of 90° peel strength with respect to the copper foil is not particularly limited, but may be, for example, 3 kN/m or less.

The procedure for measuring the 90° peel strength according to this embodiment is as follows.
First, a varnish of the above-mentioned thermosetting resin composition was applied to a 0.2 mmt whole surface etched product with an applicator at 7 mils and dried at 120° C. for 5 minutes to obtain a resin film-coated core material. obtain.
After that, YSNAP-3B (manufactured by Nippon Denshoku Co., Ltd., 3 μm thick ultra-thin copper foil with carrier copper foil) was set on the resin surface of the produced core material with resin film, and vacuum/pressurized press under the following conditions By carrying out, a substrate was obtained. (Temperature condition: heating at a temperature rising rate of 3° C./min, heating at 100° C. for 1 hour, then heating at a temperature rising rate of 3° C./min, and heating at 200° C. for 1.5 hours. Conditions: 0.4 MPa).
Thereafter, the outer layer carrier copper foil of the obtained substrate is peeled off, and an electrolytic plating film is formed on the ultrathin copper foil having a thickness of 3 μm so that the total thickness of copper is 20 μm to obtain a plated substrate.
The obtained plated substrate is heat-treated at 150° C. for 30 minutes.
After that, the above-mentioned plated substrate is subjected to an etching treatment so as to leave an electrolytically plated copper coating having a width of 10 mm to obtain a peel strength measurement sample.
The peel strength measurement sample obtained as described above can be measured for peel strength in accordance with JIS C-6481:1996.

In the present embodiment, the upper limit of the peel strength change rate of the cured product of the resin film (cured product of the thermosetting resin composition) calculated under the following conditions is, for example, 40% or less, and preferably 30%. % Or less, and more preferably 20% or less. As a result, the copper adhesion of the cured product of the resin film can be maintained even under humid atmosphere conditions, so that the SAP characteristics of the obtained insulating layer can be further improved. The lower limit of the peel strength change rate is not particularly limited, but may be 0.1% or more, for example.

In the present embodiment, the peel strength change rate can be measured, for example, by the following procedure. The peel strength measurement sample obtained by the 90 degree peel strength measurement was stored for 100 hours in an environment of 130° C. and a humidity of 85% RH. Then, the peel strength change rate represented by 100×(P ₁ −P ₂ )/P ₁ is calculated.
Here, the peel strength between the cured product and the metal foil, which is measured according to JIS C-6481: 1996 before storage, is P _1, and the measurement is performed according to JIS C-6481: 1996 after storage. The peel strength between the cured product and the metal foil is P ₂ .

The upper limit of the average linear expansion coefficient in the plane direction (XY direction) calculated in the range of 30° C. to 240° C. of the cured product of the resin film according to the present embodiment is, for example, 60 ppm/° C. or less, and preferably 55 ppm. /°C or lower, more preferably 50 ppm/°C or lower. Thereby, the warpage of the semiconductor package can be reduced. On the other hand, the lower limit of the average linear expansion coefficient (α1) is not particularly limited, but may be 1 ppm/° C. or higher, for example.

In the present embodiment, the lower limit of the glass transition temperature of the cured product of the resin film (cured product of the thermosetting resin composition) is not particularly limited, but may be, for example, 110° C. or higher, or 150° C. or higher. The temperature may be 200° C. or higher. Thereby, a cured product of the resin film having excellent heat resistance can be obtained. The upper limit of the glass transition temperature of the cured product of the resin film is not particularly limited, but may be 400° C. or lower, for example.
The glass transition temperature can be measured using a dynamic viscoelasticity analyzer (DMA). The glass transition temperature is the temperature at which the loss tangent tan δ shows the maximum value in the curve obtained by the dynamic viscoelasticity measurement under the conditions of the temperature rising rate of 5° C./min and the frequency of 1 Hz.

In the present embodiment, the glass transition temperature is 200° C., and the cured product of the resin film obtained by heat treatment for 2 hours has a frequency of 1 Hz and a heating rate of 5° C./min using, for example, a dynamic viscoelasticity measuring device. The glass transition temperature can be calculated from the measurement results obtained by conducting the dynamic viscoelasticity test under the conditions of. The dynamic viscoelasticity measuring device is not particularly limited, but, for example, a DMA device (Q800, manufactured by TA Instruments) can be used.

In the present embodiment, the maximum bending strength and the storage elastic modulus of the thermosetting resin composition are determined by, for example, appropriately selecting the types and mixing ratios of the components constituting the thermosetting resin composition. E′ ₂₅ , the bending elongation rate, and the average linear expansion coefficient can be set within desired ranges. Among these, for example, improving the dispersibility of the (meth)acrylic block copolymer, reducing the domain diameter of the polymer block phase, and the like are the maximum value of the bending strength and the storage elastic modulus E′. ₂₅ , as an element for keeping the above-mentioned bending elongation rate and the above-mentioned average linear expansion coefficient within desired numerical ranges.

(Printed wiring board)
The printed wiring board of the present embodiment is provided with 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 or a buildup layer or a solder resist layer of a normal printed wiring board, a buildup layer or a solder resist layer in a printed wiring board having no core layer, or a PLP. It can be used as an interlayer insulating layer or a solder resist layer of a coreless substrate, an interlayer insulating layer or a solder resist layer of a MIS substrate, and the like. Such an insulating layer can be preferably used also for an interlayer insulating layer or a solder resist layer that constitutes the printed wiring board in a large area printed wiring board used for collectively manufacturing a plurality of semiconductor packages. it can.

Next, an example of the printed wiring board 300 of the present embodiment will be described with reference to FIGS.
The printed wiring board 300 of the present 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). The printed wiring board 300 has a structure including an insulating layer 301 (core layer), an insulating layer 305 (buildup layer), and an insulating layer 401 (solder resist layer) as shown in FIG. 2B. 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. The core layer may be composed of a cured product obtained by curing a prepreg obtained 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 be one that does not include a fiber base material such as a glass cloth or a paper base material. Accordingly, the structure can be made particularly suitable for forming the buildup layer (interlayer insulating layer) or the solder 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 multi-layered printed wiring board. The double-sided printed wiring board is a printed wiring board in which the metal layers 303 are laminated on both surfaces of the insulating layer 301. The multilayer printed wiring board is a printed wiring board in which two or more buildup layers (for example, insulating layers 305) are laminated on the insulating layer 301 which is a core layer by a plated through hole method, a buildup method, or the like. ..

In this embodiment, the via hole 307 may be a hole for electrically connecting the layers, and may be 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 the electroless metal plating film 308.

Further, 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 a metal laminated structure of the metal foil 105 and the electrolytic metal plating layer 309, for example.
The metal layer 303 is, for example, a metal foil 105 that has been subjected to a chemical treatment or a plasma treatment, or an insulating layer (for example, the insulating layer 301 or the insulating layer 305) made of a cured product of the resin film of the present embodiment, and SAP ( It is formed by the semi-additive process) method. For example, after applying the electroless metal plating film 308 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 attached by electrolytic plating to form the plating resist. The metal layer 303 is formed by patterning the electrolytic metal plating film 309 by removing and flash etching.

Further, the printed wiring board 300 of the present embodiment can be a resin board containing no glass fiber. For example, the insulating layer 301, which is the core layer, may be configured not to contain glass fiber. Also in the semiconductor package using such a resin substrate, the linear expansion coefficient of the cured product of the resin film can be lowered, so that the warpage of the package can be sufficiently suppressed.

(Semiconductor package)
Next, the semiconductor device 400 of this embodiment will be described. 3A and 3B are cross-sectional views showing an example of the configuration of the semiconductor device 400.
The semiconductor device 400 of this embodiment may include the 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. 3A. 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. 3B. The semiconductor element 407 is covered with the 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 above flip-chip connection structure, and may have various structures. For example, a fan-out structure can be used. The insulating layer made of the cured product of the resin film of the present embodiment can suppress substrate warpage and substrate crack in the manufacturing process of the semiconductor package having the fan-out structure.

Next, a modified example of the printed wiring board of the present embodiment will be described. FIG. 4 is a process sectional view of an example of a manufacturing process of the printed wiring board 500. FIG. 4C shows a printed wiring board 500 having no core layer.
The printed wiring board 500 of the present embodiment does not include a core layer having a fiber base material, and may be a coreless resin substrate including a buildup layer and a solder resist layer, for example. It is preferable that these build-up layer and solder resist layer are 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). The buildup 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 product of the resin film of the present embodiment has excellent toughness, it is possible to suppress warpage of the printed wiring board 500 and cracks during transportation.

The metal layers 542, 552, 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, 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, after a plurality of semiconductor elements mounted on the printed wiring board 500 are collectively sealed, they are separated into a plurality of semiconductor packages. The printed wiring board 500 may be a panel board having a substantially circular shape, a rectangular shape, or the like.

The method for manufacturing the printed wiring board 500 is not particularly limited, but it can be obtained, for example, by forming a build-up layer and a 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 (eg, copper foil) are arranged on a large-area support substrate 510 (eg, 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. Then, the metal layer 542 is formed on the metal foil 530. This metal layer 542 is patterned by a usual method such as the SAP method. Subsequently, the resin film with a carrier film is laminated by a heat and pressure molding method or the like, and then the carrier base material is peeled from the resin film with a carrier film. Then, the resin film is cured. These steps are repeated three times to form two buildup layers and one solder resist layer.
After that, the supporting substrate 510 is peeled off as shown in FIG. Then, the metal foil 530 is removed by etching or the like.
As described above, the printed wiring board 500 shown in FIG. 4C is obtained.

Next, a modified example of the printed wiring board of the present embodiment will be described. FIG. 5 is a cross-sectional view showing an example of the configuration of the printed wiring board 600.
The 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 wiring board process can be used to obtain a panel size package having a larger area than a wafer. By using the PLP process, the productivity of the semiconductor package can be efficiently improved as compared with 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 the present embodiment has excellent toughness, it is possible to effectively suppress warpage of the printed wiring board 600 during the PLP process and cracks of the coreless resin substrate 610 particularly during transportation and mounting. be able to.

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

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

Further, the upper and lower surfaces of the coreless resin substrate 610 may be covered with solder resist layers (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, for example, a metal layer formed by the SAP method. The metal layer 650 may be, for example, a circuit pattern or an electrode pad.

The method of manufacturing the printed wiring board 600 of the present embodiment is not particularly limited, but the following method can be used, for example. For example, the insulating layer 612 is formed over the supporting substrate. Then, a via is formed in the insulating layer 612, and a via wiring 616 having a metal film embedded in the via is formed by a plating method. Then, a rewiring (metal layer 650) is formed on the surface of the insulating layer 612 by the SAP method. After that, a plurality of interlayer insulating layers having such interlayer connection wiring may be laminated. Then, a solder resist layer (insulating layers 630 and 632) is formed.
As described above, the printed wiring board 600 can be obtained.

Next, a modified example of the printed wiring board of the present embodiment will be described. FIG. 6 is a cross-sectional view showing an example of the configuration of the printed wiring board 700.
The printed wiring board 700 shown in FIG. 6 can be composed of a substrate with posts (MIS substrate). For example, the substrate with a post can be configured 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 substrate with posts may be a substrate after being singulated or a substrate having a large area before being singulated (for example, a support such as a wafer).
By using the printed wiring board 700 of the present embodiment, it is possible to efficiently improve the productivity of semiconductor packages to the same level or more as in 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 the present embodiment has excellent toughness, it is possible to effectively suppress warpage of the printed wiring board 700 and cracks of the coreless resin board 710 particularly during transportation and mounting.

Further, the printed wiring board 700 of the present embodiment has a large area within which a plurality of semiconductor elements (not shown) can be mounted. Then, after sealing a plurality of semiconductor elements mounted in the in-plane direction of the printed wiring board 700 in a lump and then dividing them into individual pieces, a plurality of semiconductor packages can be obtained. Since the linear expansion coefficient of the cured product of the resin film of the present embodiment can be lowered, it is possible to suppress package warpage in the obtained semiconductor package.

The printed wiring board 700 may 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. Further, the coreless resin substrate 710 can have at least the insulating layer 712 (interlayer insulating layer), the via wiring 716, and the 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 to each other through the via wiring 716. In addition, the metal layer 714 embedded in the insulating layer 712 can be connected to the metal layer 740 (electrode pad) formed on the surface of the insulating layer 712. The surface of the insulating layer 712 may have a polished surface. One surface of the metal layer 718 may be flush with the polishing surface of the insulating layer 712.

In the printed wiring board 700 of the present embodiment, the coreless resin substrate 710 is composed of a single-layer interlayer insulating layer, but is not limited to this structure and has a structure in which a plurality of interlayer insulating layers are laminated. May be. Via wires 716 and metal layers 718 (posts) may be formed as interlayer connection wires in such an interlayer insulating layer. Further, 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. Further, the upper and lower surfaces of the coreless resin substrate 710 may be covered with solder resist layers (insulating layers 730 and 732).

The method of manufacturing the printed wiring board 700 of the present embodiment is not particularly limited, but the following method can be used, for example. For example, a copper post (eg, the metal layer 718) is formed over the insulating layer over the supporting substrate. The copper post is further embedded with an insulating layer. Then, the surface of the copper post is exposed by a method such as grinding or chemical etching (that is, the copper post is cued). Subsequently, rewiring is formed by the SAP method. Through these steps, the coreless resin substrate 710 having the interlayer insulating layer can be formed. After that, the step of forming the interlayer insulating layer may be repeated a plurality of times to stack a plurality of interlayer insulating layers having interlayer connecting wirings. Then, solder resist layers (insulating layers 730 and 732) are formed.
As described above, the printed wiring board 700 can be obtained.

Although the embodiments of the present invention have been described above with reference to the drawings, these are merely examples of the present invention, and various configurations other than the above may be adopted.

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

(Preparation of thermosetting resin composition)
Varnish-like thermosetting resin compositions were prepared for Examples and Comparative Examples.
First, each component was dissolved or dispersed at a solid content ratio shown in Table 1, adjusted to have a nonvolatile content of 70% by weight with methyl ethyl ketone, and stirred using a high-speed stirring device to prepare a resin varnish.
In addition, the numerical value showing the compounding ratio of each component in Table 1 has shown the compounding ratio (weight%) of each component with respect to the whole solid of the thermosetting resin composition.
The details of the raw materials for each component in Table 1 are as follows.
In the examples and comparative examples, the following raw materials were used.
(Thermosetting resin)
Thermosetting resin 1: Bisphenol A epoxy resin (DIC, EPICLON, 840S)
Thermosetting resin 2: Bisphenol F type epoxy resin (manufactured by DIC Corporation, EPICLON, 830S)
Thermosetting resin 3: naphthalene skeleton-modified cresol novolac type epoxy resin (HP-5000 manufactured by DIC Corporation)
(Curing agent)
First curing agent 1: MDEA (4,4'-methylenebis(2,6-diethylaniline), manufactured by Lonza, Lonza Cure M-DEA kr)
First curing agent 2: SB-AA (4,4′-methylenebis(2-ethylaniline), Nippon Kayaku Co., Ltd., SB-AA).
Curing agent 1: DDS (4,4'-diaminodiphenyl sulfone, 4,4'-DAS manufactured by Mitsui Fine Chemicals, Inc.)
Hardener 2: Dicyandiamide (DIZY7, manufactured by Mitsubishi Chemical Corporation)
First curing agent 3: Phenolic curing agent (Nippon Kayaku Co., GPH103)
First curing agent 4: Phenolic curing agent (phenol novolac resin, Sumitomo Bakelite Co., PR-HF-3))
(Inorganic filler)
Inorganic filler 1: Silica particles (manufactured by Admatex, SC4050, average particle size 1.1 μm)
((Meth)acrylic block copolymer)
(Meth)acrylic block copolymer 1: (block copolymer of acrylic monomer (PMMA-b-PBA-b-PMMA; b=block), number average molecular weight: about 15,000, manufactured by Arkema, Nano Strength M52)
(Meth)acrylic block copolymer 2: (block copolymer of acrylic monomer (PMMA-b-PBA-b-PMMA; b=block), number average molecular weight: about 15,000, manufactured by Arkema, Nano Strength M52N)
(Curing accelerator)
Curing accelerator 1: 2-phenylimidazole (2PZ-PW manufactured by Shikoku Kasei)
(Coupling agent)
Coupling agent 1: Silane coupling agent (N-phenyl γ-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., KBM-573)

(Resin film with carrier)
In Examples and Comparative Examples, the obtained resin varnish was applied on a PET film as a carrier substrate, and then the solvent was removed under the conditions of 120° C. for 5 minutes to form a resin film having a thickness of 25 μm. As a result, a resin film with a carrier was obtained.

(Manufacturing of semiconductor package)
1. Manufacture of printed wiring board Double-sided copper clad laminate (Sumitomo Bakelite Co., Ltd., LAZ-4785TH-G, insulating layer thickness 0) using ultra-thin copper foil (Mitsui Mining & Smelting Co., Ltd., Microthin Ex, 2.0 μm) After performing a roughening treatment of about 1 μm on the ultra-thin copper foil layer on the surface of 0.2 mm, a through hole of φ80 μm for interlayer connection was formed by a carbon dioxide laser. Then, it is dipped in a swelling solution at 60°C (Atotech Japan Co., Swelling Dip Securigant P) for 5 minutes, and further at 80°C in an aqueous potassium permanganate solution (Atotech Japan, Concentrate Compact CP) for 2 minutes. Then, it neutralized and the desmear process in the through hole was performed. Next, electroless copper plating was performed with a thickness of 0.5 μm to form a resist layer for electrolytic copper plating with a thickness of 18 μm, pattern copper plating was performed, and heating was performed at 150° C. for 30 minutes to perform post cure. Next, the plating resist was peeled off and the entire surface was flash-etched to form a circuit pattern on both sides of L/S=15/15 μm.
The resin film with a carrier obtained as described above (as an interlayer insulating film) is laminated on both sides of the circuit board after the circuit pattern is formed so that the resin film faces the circuit pattern, and then the two-stage vacuum pressure type Using a laminator device (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.), the pressure is reduced to 10 hPa or less for 30 seconds, the temperature is 120° C. as one stage condition, the pressure is 0.8 MPa, 30 seconds, and the temperature is a SUS end plate as two stage conditions. Vacuum heating and pressure molding were performed at 120° C. and a pressure of 1.0 MPa for 60 seconds. Next, after peeling the carrier base material from the resin film with carrier, the resin film on the circuit pattern was cured at 200° C. for 2 hours. Then, a circuit was processed by a semi-additive method, the resin film with a carrier obtained as described above (as a solder resist layer) was similarly laminated on both sides, and laser opening was performed to obtain a printed wiring board.

2. Manufacturing of semiconductor device A semiconductor element with a solder bump having a thickness of 10 mm×10 mm×100 μm is mounted on the obtained printed wiring board, sealed with underfill (CRP-4160G manufactured by Sumitomo Bakelite Co., Ltd.), and at 150° C. It was cured for 2 hours. Finally, a semiconductor device was obtained by dicing into 15 mm×15 mm.

In the examples and comparative examples, the following evaluations were performed on the resin plate, core material, and semiconductor package. The evaluation results are shown in Table 2.

(Cured product)
Four pieces of the PET film, which is a carrier base material, were peeled off from the obtained resin film with carrier, and laminated to form a resin sheet having a thickness of 100 μm. Then, the resin sheet was heat-treated at 200° C. for 2 hours to obtain a cured product of the thermosetting resin composition.

(Domain diameter of polymer block layer)
The obtained cured product was made into a thin film by a microtome, and then the domain diameter was calculated by image analysis of a dyed sample with a transmission electron microscope.
No bleed was observed on the surface of the cured products of Examples 1 to 7. On the other hand, bleeding was observed on the surface of the cured products of Comparative Examples 1 and 2.

(Three-point bending test)
The obtained resin varnish was heated at 100° C. for 1 hour and then at 200° C. for 2 hours to obtain a cured product of the thermosetting resin composition shown in Table 1. The cured product was cut into a test piece having a length of 50 mm and a width of 10 mm.
In the three-point bending test, the test piece was placed on two fulcrums arranged at a constant distance, and a load was applied to one point in the center between the fulcrums. At this time, using a precision universal tester (manufactured by Shimadzu Corporation, Autograph AG-IS), the distance L between the two fulcrums is 5 mm, the thickness of the test piece is 0.1 mm, the measurement temperature is 25° C., and the test speed is 1 mm. The condition of /min was used.
In the above three-point bending test, the maximum value of the bending strength is the value of the stress when the bending load is maximum under the above conditions, and the storage elastic modulus E′ is the test force in the range of 0.5N to 1.0N. The bending elongation was determined by the following equation. Elongation rate (%): (formula) 600 x (deflection amount (displacement) until the test piece breaks) x (test piece thickness)/(distance between fulcrums) ²

(Average linear expansion coefficient (30 to 240°C))
A test piece of 4 mm x 40 mm was cut out from the obtained cured product, and a temperature range of 30 to 260°C and a heating rate were used for the test piece using a thermomechanical analyzer TMA (TA Instruments, Q400). Two cycles of thermomechanical analysis (TMA) were measured under the conditions of 10° C./min, load of 10 g and tensile mode. The average value of the linear expansion coefficient in the plane direction (XY direction) in the range of 30°C to 240°C was calculated. The value of the second expansion was used as the coefficient of linear expansion.

(Peel strength)
First, the obtained resin varnish was applied to a 0.2 mmt whole surface etched product at 7 mils using an applicator and dried at 120° C. for 5 minutes to obtain a resin film-coated core material.
After that, YSNAP-3B (manufactured by Nippon Denshoku Co., Ltd., 3 μm thick ultra-thin copper foil with carrier copper foil) was set on the resin surface of the produced core material with resin film, and vacuum/pressurized press under the following conditions. By carrying out, a substrate was obtained. (Temperature condition: The temperature was raised at a rate of 3° C./min, heated at 100° C. for 1 hour, then raised at a rate of 3° C./min, and heated at 200° C. for 1.5 hours. Conditions: 0.4 MPa).
Thereafter, the outer layer carrier copper foil of the obtained substrate was peeled off, and an electrolytic plating film was formed on the 3 μm-thick ultrathin copper foil so that the total copper thickness was 20 μm, to obtain a plated substrate.
The obtained plated substrate was heat-treated at 150° C. for 30 minutes.
Then, the above-mentioned plated substrate was subjected to an etching treatment so as to leave an electrolytically-plated copper coating having a width of 10 mm to obtain a peel strength measurement sample.
The peel strength measurement sample obtained above was subjected to peel strength measurement in accordance with JIS C-6481:1996.

(Peel strength change rate)
The obtained peel strength measurement sample was stored in an environment of 130° C. and a humidity of 85% RH for 100 hours. Then, the peel strength change rate represented by 100×(P ₁ −P ₂ )/P ₁ was calculated.
Here, the peel strength between the cured product and the metal foil, which is measured according to JIS C-6481: 1996 before storage, is P _1, and the measurement is performed according to JIS C-6481: 1996 after storage. is the, the peel strength between the cured product and the metal foil was P _2.

(Glass-transition temperature)
A test piece of 8 mm×40 mm was cut out from the obtained cured product, and dynamic viscoelasticity measurement was performed on the test piece at a temperature rising rate of 5° C./min and a frequency of 1 Hz. The glass transition temperature was measured by dynamic viscoelasticity measurement (DMA device, TA Instruments, Q800). Here, the glass transition temperature is a temperature at which the loss tangent tan δ shows the maximum value.

(Panel warp)
A 12 μm copper foil is placed on a support substrate of 250 mm long×250 mm square SUS, and the resin film with a carrier film obtained in Examples and Comparative Examples is treated with a two-stage vacuum pressure laminator device (manufactured by Meiki Seisakusho Co., Ltd., MVLP-500), the pressure is reduced for 30 seconds and is 10 hPa or less, the temperature is 120° C., the pressure is 0.8 MPa, and the pressure is 0.8 MPa for 30 seconds as the one-stage condition. It was vacuum heated and pressed in seconds. Then, the carrier base material was peeled from the resin film with carrier, and then cured at 180° C. for 2 hours. This was repeated three times to form a three-layer build-up layer, and the panel warp when peeling off SUS was evaluated.
The warp of the plate edge was measured ◎: Less than 15 mm ○: 15 mm or more and less than 50 mm (substantially no problem)
X: 50 mm or more

(Handling property)
After peeling SUS, further etch 12 μm copper foil. After that, the presence or absence of cracks in the panel was evaluated.
○: no cracks ×: cracks

(Interlayer insulation reliability)
First, roughening treatment (CZ treatment, 1 μm) was performed on a 12 μm-thick copper foil on the surface of a double-sided copper-clad laminate (LAZ-4785TH-G, manufactured by Sumitomo Bakelite Co., Ltd., insulating layer thickness 0.2 mm).
Then, the obtained resin varnish was applied with an applicator at 5 mils and dried at 120° C. for 5 minutes to obtain a resin-coated core material.
Then, a 12 μm thick copper foil was set on the resin surface of the produced core material with a resin film, and vacuum/pressurizing was performed under the following conditions to obtain a substrate. (Temperature condition: The temperature was raised at a rate of 3° C./min, heated at 100° C. for 1 hour, then raised at a rate of 3° C./min, and heated at 200° C. for 1.5 hours. Conditions: 0.4 MPa).
Then, a 12 μm-thick copper foil was subjected to an etching treatment while leaving 10 mmΦ copper, to obtain a test sample.
Using this test sample, the insulation resistance in continuous humidity was evaluated under the conditions of a temperature of 130° C., a humidity of 85% and an applied voltage of 3.3V. A resistance value of 10 ⁶ Ω or less was regarded as a failure. The evaluation criteria are as follows.
◯: No failure for 500 hours or more △: Failure for 200 hours or more and less than 500 hours ×: Failure for less than 200 hours

Although the present invention has been described more specifically based on the embodiments, these are merely examples of the present invention, and various configurations other than those described above can be adopted.

10 resin film 12 carrier base material 100 resin film 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 encapsulant layer 500 printed wiring board 510 support substrate 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 714 metal layer 716 via Wiring 718 Metal layer 720 Semiconductor element 730 Insulating layer 732 Insulating layer 740 Metal layer

Claims (17)

A thermosetting resin composition used for forming an insulating layer in a printed wiring board,
A thermosetting resin,
Hardener,
An inorganic filler,
Including a (meth)acrylic block copolymer,
The thermosetting resin composition, wherein the curing agent contains at least one first curing agent having a Hansen solubility parameter distance of 16 MPa1/2 or less from the (meth)acrylic block copolymer. The thermosetting resin composition according to claim 1, wherein
In the cured product of the thermosetting resin composition, a micro phase separation structure in which a polymer block phase of the (meth)acrylic block copolymer is dispersed in a matrix phase formed by curing the thermosetting resin. The thermosetting resin composition in which is formed. The thermosetting resin composition according to claim 2, wherein
The thermosetting resin composition, wherein the domain diameter of the polymer block phase is 200 nm or less. The thermosetting resin composition according to any one of claims 1 to 3,
The thermosetting resin composition, wherein the first curing agent contains an amine curing agent or a curing agent having a hydroxyl group. The thermosetting resin composition according to any one of claims 1 to 4,
The (meth)acrylic block copolymer is
A diblock copolymer having a structure in which a polymer block (S) and a polymer block (H) having a glass transition temperature (Tg) higher than that of the polymer block (S) are arranged side by side,
A copolymer having the polymer blocks (S) and the polymer blocks (H) alternately arranged, and the polymer blocks (S) in the middle, and the polymer blocks (S) are provided at both ends with the copolymer. A thermosetting resin composition containing one or more selected from triblock copolymers having a polymer block (H). The thermosetting resin composition according to any one of claims 1 to 5,
The thermosetting resin composition, wherein the (meth)acrylic block copolymer has a number average molecular weight (Mn) of 3,000 or more and 500,000 or less. The thermosetting resin composition according to any one of claims 1 to 6,
Thermosetting resin composition whose content of the said inorganic filler is 50 weight% or more and 90 weight% or less with respect to the said thermosetting resin composition whole. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition comprises:
A thermosetting resin composition, wherein the inorganic filler contains silica. The thermosetting resin composition according to any one of claims 1 to 8, wherein
A thermosetting resin composition, wherein the thermosetting resin contains an epoxy resin. The thermosetting resin composition according to any one of claims 1 to 9,
A thermosetting resin composition further comprising a coupling agent. The thermosetting resin composition according to any one of claims 1 to 10,
The thermosetting resin composition, wherein the cured product of the thermosetting resin composition has an average coefficient of linear expansion calculated in the range of 30°C to 240°C of 1 ppm/°C or more and 60 ppm/°C or less. The thermosetting resin composition according to any one of claims 1 to 11,
The thermosetting resin composition, wherein the cured product of the thermosetting resin composition has a 90° peel strength of 0.5 kN/m or more with respect to the copper foil. The thermosetting resin composition according to any one of claims 1 to 12,
A thermosetting resin composition, wherein the cured product of the thermosetting resin composition has a glass transition temperature of 110° C. or higher. The thermosetting resin composition according to any one of claims 1 to 13,
The printed wiring board is a thermosetting resin composition containing no glass fiber. A carrier substrate,
A resin film with a carrier, comprising: a resin film provided on the carrier base material, the resin film comprising the thermosetting resin composition according to any one of claims 1 to 14. A printed wiring board comprising an insulating layer made of a cured product of the thermosetting resin composition according to claim 1. A printed wiring board according to claim 16,
A semiconductor device mounted on a circuit layer of the printed wiring board or built in the printed wiring board.

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