JP6819067B2 - 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.

Various developments have been made on the epoxy resin compositions so far from the viewpoint of mechanical properties. Examples of this type of technique include the epoxy resin composition described in Patent Document 1. According to the same document, a poly (methyl methacrylate) / poly (butyl acrylate) / poly (methyl methacrylate) triblock copolymer is used from the viewpoint of fracture toughness of the cured product of the epoxy resin composition (Patent). Document 1 paragraph 0021).

JP-A-2015-178630

However, in recent years, the area of the semiconductor package manufacturing process tends to increase. As a result of examination by the present inventor based on such a development environment, the cured product of the epoxy resin composition described in the above document has room for improvement in terms of production stability when used in the above production process. It turned out to be.

The present inventor has found that during a panel-level process of manufacturing a large-area panel-sized package, the panel substrate is warped and cracks occur during transportation and mounting. As a result of further examination focusing on this point, it was found that the degree of suppression of warpage and cracks of the panel substrate can be evaluated by using the bending strength measured by the three-point bending test of the insulating layer used for the panel substrate as an index. did.

As a result of diligent studies based on such findings, as a result of further diligent research on the above indicators, it is possible to prevent warpage and cracks of the panel substrate during the above-mentioned panel level process by setting the bending strength to a predetermined value or more. We have found that the stability can be improved, and have completed the present invention.

According to the present invention
A thermosetting resin composition used for forming an insulating layer in a printed wiring board.
Thermosetting resin and
Hardener and
Inorganic filler and
Contains (meth) acrylic block copolymers,
The thermosetting resin composition is a microphase in which the polymer block phase of the (meth) acrylic block copolymer is dispersed in a matrix phase obtained by curing the thermosetting resin in the cured product. A separated structure is formed,
Provided is a thermosetting resin composition having a maximum bending strength of 70 MPa or more and 1000 MPa or less in a cured product of the thermosetting resin composition measured by a three-point bending test under the following conditions.
(Three-point bending test)
The thermosetting resin composition is 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. This cured product is cut into a test piece having a length of 50 mm and a width of 10 mm. The obtained test piece is placed on two fulcrums arranged at a fixed distance, and an evaluation is performed in which a load is applied to one point in the center between the fulcrums. At this time, the conditions of the distance L between the two fulcrums: 5 mm, the thickness of the test piece: 0.1 mm, the measurement temperature: 25 ° C., and the test speed: 1 mm / min are used.

Further, according to the present invention.
Carrier base material and
Provided is a resin film with a carrier, which comprises a resin film made of the thermosetting resin composition provided on the carrier base material.

Further, according to the present invention.
Provided is a printed wiring board provided with an insulating layer composed of a cured product of the thermosetting resin composition.

Further, according to the present invention.
With the above printed wiring board
Provided is a semiconductor device including a semiconductor element mounted on a circuit layer of the printed wiring board or built in the printed wiring board.

According to the present invention, there is provided a thermosetting resin composition capable of obtaining an insulating layer having excellent production stability, a resin film with a carrier using the same, a printed wiring board, and a semiconductor device.

It is sectional drawing which shows an example of the structure of the resin film with a carrier in this embodiment. It is sectional drawing which shows an example of the structure of the printed wiring board in this embodiment. It is sectional drawing which shows an example of the structure of the semiconductor device in this embodiment. It is a process sectional view which shows an example of the manufacturing process of the printed wiring board in this embodiment. It is sectional drawing which shows an example of the structure of the printed wiring board in this embodiment. It is sectional drawing which shows an example of the 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 drawings, similar components are designated by the same reference numerals, and description thereof will be omitted as appropriate.

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 heat measured by a three-point bending test. The maximum value of the bending strength of the cured product of the curable resin composition can be 70 MPa or more and 1000 MPa or less. Such a thermosetting resin composition is used for forming an insulating layer in a printed wiring board.

As a result of examining a printed wiring board (hereinafter, may be referred to as a panel board) in a panel level process for manufacturing a large-area panel size package, the present inventor has found that the panel board is warped and during transportation and mounting. In, we focused on the occurrence of cracks in the panel substrate.

Based on this point of view, a further study was made on the thermosetting resin composition used for forming the insulating layer on the panel substrate, and it was found that warpage and cracks of the panel substrate could be suppressed by increasing the strength of the insulating layer. It was. As a result of the examination based on this knowledge, it was found that the suppression of warpage and cracks of the panel substrate can be evaluated by using the bending strength measured by the three-point bending test of the insulating layer used for the panel substrate as an index.

As a result of further diligent research on the above indicators, it was found that by setting the maximum value of bending strength to 100 MPa or more, warpage and cracks of the panel substrate during the above-mentioned panel level process can be prevented, and manufacturing stability can be improved. Has been completed.

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

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, and is used, for example, for a build-up layer, a solder resist layer, and 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 used, an interlayer insulating layer or a solder resist layer of a MIS substrate, or the like. As described above, the cured product of the resin film of the present embodiment is used in a large-area printed wiring board used for collectively producing a plurality of semiconductor packages, such as an interlayer insulating layer or a solder resist constituting the printed wiring board. It can also be suitably used for layers.

By using the cured product of the resin film made of the thermosetting resin composition of the present embodiment as the insulating layer, the toughness is excellent. Therefore, the panel warps during the panel level process for manufacturing a large-area panel size package. In addition, it is possible to suppress substrate cracks during transportation and mounting.

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, and an inorganic filler.

(Thermosetting resin)
Examples of the thermosetting resin include epoxy resins, maleimide compounds, benzoxazine compounds and the like. These may be used alone or in combination of two or more. In the present 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, and bisphenol M type epoxy resin (4,4'-(1,3-phenylenediiso). Pridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,5'-cyclohexy) Bisphenol type epoxy resin such as dienbisphenol 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, etc. Novorak type epoxy resin; Biphenyl type epoxy resin; Xylylene type epoxy resin, Biphenyl aralkyl type epoxy resin and other aralkyl type epoxy resin; Naftylene 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; norbornen type epoxy resin; adamantan type epoxy resin; Examples include type epoxy resins.

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

Among the epoxy resins, bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthalene type epoxy resin, from the viewpoint of further improving the heat resistance and insulation reliability of the obtained printed wiring substrate, One or more selected from the group consisting of anthracene type epoxy resin and dicyclopentadiene type epoxy resin is preferable, from aralkyl type epoxy resin, novolac type epoxy resin having a fused ring aromatic hydrocarbon structure, and naphthalene type epoxy resin. One or more selected from the group is more preferable.

As the bisphenol A type epoxy resin, "Epicoat 828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation can be used. As the bisphenol F type epoxy resin, "jER806H" and "YL983U" manufactured by Mitsubishi Chemical Corporation, "EPICLON 830S" manufactured by DIC Corporation, and the like can be used. As the bifunctional naphthalene type epoxy resin, "HP4032", "HP4032D", "HP4032SS" and the like manufactured by DIC Corporation 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., or the like can be used. As an aralkyl type epoxy resin, "NC3000", "NC3000H", "NC3000L", "NC3000S", "NC3000SH", "NC3100" manufactured by Nippon Kayaku Co., Ltd., and "ESN-170" manufactured by Nippon Steel Chemical Co., Ltd. , And "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-7311", "EXA-7311L", "EXA7311-G3" and the like manufactured by DIC Corporation can be used.

Among these epoxy resins, the aralkyl type epoxy resin is particularly preferable. Thereby, the heat resistance and flame retardancy of the cured product of the resin film can be further improved.

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 above general formula (1), A and B represent aromatic rings such as a benzene ring and a biphenyl structure. Hydrogen in the aromatic rings of A and B may be substituted. As the substituent, For example, a methyl group, an ethyl group, a propyl group, a phenyl group and the like can be mentioned. N represents a repeating unit, for example, an integer of 1 to 10).

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

（式（１ａ）中、ｎは、１〜５の整数を示す。）

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

（式（１ｂ）中、ｎは、１〜５の整数を示す。）

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

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

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

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

The phenolic compound is not particularly limited, but for example, phenol; cresols such as o-cresol, m-cresol, p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2, Xylenols such as 6-xylenol, 3,4-xylenol, 3,5-xylenol; trimethylphenols such as 2,3,5 trimethylphenol; ethyl such as o-ethylphenol, m-ethylphenol, p-ethylphenol Phenols; Alkylphenols such as isopropylphenol, butylphenol, t-butylphenol; phenylphenols such as o-phenylphenol, m-phenylphenol, p-phenylphenol; 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, Naphthalene diols such as 2,7-dihydroxynaphthalene; polyhydric phenols such as resorcin, catechol, hydroquinone, pyrogallol, fluoroglucin; alkyl polyhydric phenols such as alkylresorcin, alkylcatechol, alkylhydroquinone can be mentioned. Of these, phenol is preferable from the viewpoint of cost and the effect on the decomposition reaction.

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

The fused ring aromatic hydrocarbon compound is not particularly limited, but for example, naphthalene derivatives such as methoxynaphthalene and butoxynaphthalene; anthracene derivatives such as methoxyanthracene; phenanthrene derivatives such as methoxyphenanthrene; other tetracene derivatives; chrysene derivatives; pyrene derivatives; Examples thereof include triphenylene derivatives; tetraphene derivatives and the like.

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

(In the above general formula (V), Ar is a fused ring aromatic hydrocarbon group, and R may be the same or different from each other. Hydrogen atom; hydrocarbon group having 1 or more and 10 or less 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, n, p, and q are integers of 1 or more, and the values of p and q are for each repeating unit. May be the same or different.)
Further, Ar in the formula (V) may have a structure represented by (Ar1) to (Ar4) in the following formula (VI).

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

Further, as the epoxy resin other than the above, a naphthalene type epoxy resin such as a naphthalene type epoxy resin, a naphthalene diol type epoxy resin, a bifunctional to tetrafunctional naphthalene type epoxy resin, and a naphthalene ether type epoxy resin is preferable. As a result, the heat resistance and low thermal expansion of the obtained printed wiring board can be further improved. Here, the naphthalene type epoxy resin refers to a resin having a naphthalene ring skeleton and having two or more glycidyl groups.
Further, since the π-π stacking effect of the naphthalene ring is higher than that of the benzene ring, the naphthalene type epoxy resin is particularly excellent in low thermal expansion and low thermal shrinkage. Further, since the polycyclic structure has a high rigidity effect and the glass transition temperature is particularly high, the change in heat shrinkage before and after reflow is small. 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 to tetrafunctional naphthalene type epoxy resin is the following formula (VII-3). (VII-4) (VII-5), the naphthalene ether type epoxy resin can be represented by, for example, 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 indicates an average number of 1 or more and 6 or less, and R indicates a glycidyl group or a hydrocarbon group having 1 or more and 10 or less 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 either o or m is 1 or more.)

The lower limit of the weight average molecular weight (Mw) of the epoxy resin is not particularly limited, but may be Mw300 or more, preferably Mw800 or more. When Mw is at least the above lower limit value, it is possible to suppress the occurrence of tackiness in 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 handleability is improved and it becomes easy to form the resin film. The Mw of the epoxy resin can be measured by, for example, GPC.

The lower limit of the epoxy resin content is preferably 3% by weight or more, more preferably 4% by weight or more, and 5% by weight, based on 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 above lower limit value, the handleability is improved and it becomes easy to form the resin film. On the other hand, the upper limit of the epoxy resin content is not particularly limited with respect to the entire thermosetting resin composition (total solid content excluding the solvent), but for example, it is preferably 60% by weight or less, preferably 45% by weight or less. More preferably, it is more preferably 30% by weight or less. When the content of the epoxy resin is not more than the above upper limit value, the strength and flame retardancy of the obtained printed wiring board are improved, the coefficient of linear expansion of the printed wiring board is lowered, and the effect of reducing warpage is improved. In some cases.
The total solid content of the thermosetting resin composition refers to all the components excluding the solvent contained in the thermosetting resin composition. Hereinafter, the same applies to the present specification.

((Meta) acrylic block copolymer)
The thermosetting resin composition of the present embodiment can contain a (meth) acrylic block copolymer. According to this embodiment, by sufficiently dispersing the (meth) acrylic block copolymer, the toughness of the obtained insulating layer is enhanced, and the adhesion with other members such as a circuit layer is further improved. Can be done.

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 monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and n-methacrylate. (Meta) acrylic acid alkyl esters 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. Estel; (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, maleine anhydride A carboxyl group-containing acrylic monomer having a carboxyl group in a molecule such as an acid; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate A hydroxyl group-containing acrylic monomer having a hydroxyl group in a molecule such as hydroxypropyl, 4-hydroxybutyl methacrylate, mono (meth) acrylic acid ester of glycerin; glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl. Acrylic monomer having an epoxy group in a molecule such as methacrylate; Allyl group-containing acrylic monomer having an allyl group in a molecule such as allyl acrylate and allyl methacrylate; γ-methacryloyloxypropyltrimethoxysilane, γ- A silane group-containing acrylic monomer having a hydrolyzable silyl group in a molecule such as methacryloyloxypropyltriethoxysilane; benzo such as 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole. Examples thereof include an ultraviolet-absorbing acrylic monomer having a triazole-based ultraviolet-absorbing group. These may be used alone or in combination of two or more.

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

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

Among these, as the (meth) acrylic block copolymer, the 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 diblock copolymer having an HS structure in which polymer blocks (H) (hard blocks) having a Tg higher than that of the polymer block (S) are lined up, a polymer block (S) and a polymer block ( A copolymer in which H) is alternately arranged, a triblock copolymer having an HSH structure having a polymer block (S) in the middle and polymer blocks (H) at both ends thereof, and the like 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 less than 30 ° C. 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 be different. 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 may be different. Good.

The monomer component constituting the polymer block (H) is not particularly limited, and 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 acrylic acid C _2-10 alkyl ester such as butyl acrylate and 2-ethylhexyl acrylate, and butadiene (1,4-butadiene).

A preferable specific example of the (meth) acrylic block copolymer is, for example, a polymer in which the polymer block (S) is composed of butyl acrylate (BA) as a main monomer, and the polymer block (H). Is a polymer composed of methyl methacrylate (MMA) as a main monomer, polymethyl methacrylate-block-polybutyl acrylate-block-polymethyl methacrylateer polymer (PMMA-b-PBA-b-PMMA), PMMA-b. -PBA and the like can be mentioned.
The PMMA-b-PBA-b-PMMA and PMMA-b-PBA are preferable in terms of improving heat resistance, light resistance, and crack resistance. The PMMA-b-PBA-b-PMMA and PMMA-b-PBA have hydrophilic groups (for example, hydroxyl groups, carboxyl groups, etc.) for the purpose of improving compatibility with thermosetting resins and the like, if necessary. A monomer having (amino group, etc.), for example, hydroxyethyl (meth) acrylic acid, hydroxypropyl (meth) acrylic acid, (meth) acrylic acid, etc., is copolymerized with PMMA block and / or PBA block. May be 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, and 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 value, the toughness of the obtained cured product can be made better, and as a result, the 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 value, the compatibility with the thermosetting resin can be improved.

The (meth) acrylic block copolymer can be produced by a known or conventional method for producing a block copolymer.
Examples of the (meth) acrylic block copolymer include the trade names "Nanostrength M52N", "Nanostrength M22N", "Nanostrength M51", "Nanostrength M52", "Nanostrength M52N", and "Nano". "Strength M53", "Nanostrength M22" (Arkema, PMMA-b-PBA-b-PMMA), product name "Nanostrength D51N" (Arkema, PMMA-b-PBA), product name "Nanostrength E21" , "Nanostrength E41" (manufactured by Arkema, PSt (polystyrene) -b-PBA-b-PMMA) and other commercially available products can also be used.

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

(Hardener)
The thermosetting resin composition of the present embodiment may contain a curing agent.
The curing agent according to the present embodiment may contain at least one first curing agent having a Hansen solubility parameter distance (HSP distance) of 16 MPa ^1/2 or less from the (meth) acrylic block copolymer. preferable. As a result, the toughness of the cured product of the thermosetting resin composition can be further 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 breaking energy in the cured product of the thermosetting resin composition is in a uniform state. It can be present and is believed to improve the toughness of the cured product.

Hansen's Solubility Parameter (HSP) is an indicator of how soluble a substance is 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 polarity term (δ _p ), and a hydrogen bond term (δ _h ). And it can be judged that those having similar vectors have high solubility. It is possible to judge the similarity of vectors by the distance of Hansen solubility parameter (HSP distance).

Here, the computer software HSPiP developed by Hansen and Abbott includes a function to calculate the HSP distance and a database describing various resin and solvent or non-solvent Hansen parameters. The Hansen solubility parameter (HSP value) used in the present specification can be calculated by using software called HSPiP (Hansen Solubility Parameters in Practice). For example, the values described in the Solvent list and the Polymer list included in the HSPiP 3rd version may be corrected to 25 ° C. with reference to them. Here, the resin and solvent or non-solvent not described in 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 represented by 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, for example, 1 MPa ^1/2 or more.

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 can be reduced. Can be done. 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 polarity 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 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 polarity 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. The mechanism is unknown, but it is thought that the contact between the first curing agent and the (meth) acrylic block copolymer reduces 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 ^1/2 or less. The lower limit of the dispersion term (D) of HSP is not particularly limited, but may be, for example, 1 MPa ^1/2 or more.

Further, as the first curing agent, an amine curing agent having an amino group may be used. As the amine curing agent, for example, an amine curing agent having a diphenylmethane skeleton may be used.
Further, as the first curing agent, a curing agent having a hydroxyl group may be used. 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 novolak skeleton may be used. Thereby, the chemical resistance can be improved.

In the present embodiment, the upper limit of the distance (HSP distance) of the amine curing agent, which is the first curing agent, from the Hansen solubility parameter 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 in combination. The second curing agent is not particularly limited, but is, for example, a tertiary amine compound such as benzyldimethylamine (BDMA), 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 Examples include imidazole compounds such as -2-phenylimidazole (1B2PZ); catalytic curing agents such as Lewis acid such as BF ₃ complex.
Also, for example, aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylerylene diamine (MXDA), m-phenylenediamine, p-phenylenediamine, o-xylenediamine, 4,4'-. Diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 4,4'- (P-phenylenediisopropyridene) dianiline, 2,2- [4- (4-aminophenoxy) phenyl] propane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3 , 3'-diethyl-5,5'-dimethyldiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane and other aromatic polyamines, as well as polyamine compounds containing disyandiamide (DICY), organic acid dihydralide and the like; Hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA) and other alicyclic acid anhydrides, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA) and the like. Acid anhydrides including aromatic acid anhydrides; Polymercaptan compounds such as polysulfide, thioester and thioether; Isocyanate compounds such as isocyanate prepolymer and blocked isocyanate; Heavy addition type such as organic acids such as carboxylic acid-containing polyester resin Hardener; 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, as the second curing agent, for example, a phenol resin-based curing agent such as a novolak type phenol resin or a resol type phenol resin; a urea resin such as a methylol group-containing urea resin; a melamine resin such as a methylol group-containing melamine resin, etc. A condensation type curing agent of the above may also be used. These may be used alone or in combination of two or more.

The 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. For example, phenol novolac resin and cresol. Novolak-type phenolic resins such as novolak resin and naphthol novolak resin; polyfunctional phenolic resins such as triphenolmethane-type phenolic resin; modified phenolic resins such as terpen-modified phenolic resin and dicyclopentadiene-modified phenolic resin; phenylene skeleton and / or biphenylene Examples thereof include phenol aralkyl resins having a skeleton, phenylene and / or aralkyl-type resins such as naphthol aralkyl resin having a biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F. These may be used alone or in combination of two or more. Of 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 value or more, problems such as tackiness of the prepreg are less likely to occur, and by setting the weight average molecular weight to the above upper limit value or less, the impregnation property into 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 for example, 0.01% by weight or more is preferable, and 0.05% by weight or more is preferable. More preferably, 0.2% by weight or more is further preferable. By setting the content of the curing agent to the above lower limit value or more, the effect of promoting curing can be sufficiently exhibited. On the other hand, the upper limit of the content of the curing agent is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, but is preferably 25% by weight or less, more preferably 20% by weight or less, for example. , 15% by weight or less is more preferable. When the content of the curing agent is not more than 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, preferably 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 for example, it is preferably 25% by weight or less, preferably 20% by weight or less. More preferably, 15% by weight or less is further preferable. Thereby, the balance with other second curing agents can be improved.

(Inorganic filler)
The thermosetting resin composition of the present embodiment may contain an inorganic filler.
Examples of the inorganic filler include silicates such as talc, fired clay, unburned clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, silica, and molten silica; calcium carbonate, magnesium carbonate, and hydro. Carbonates such as tarcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide; sulfates or sulfates such as barium sulfate, calcium sulfate, calcium sulfite; zinc borate, barium metaborate, boric acid Borates such as aluminum, calcium borate, sodium borate; nitrides such as aluminum hydroxide, boron nitride, silicon nitride, carbon nitride; titanates such as strontium titanate and barium titanate can be mentioned.
Among these, talc, alumina, glass, silica, mica, aluminum hydroxide and magnesium hydroxide are preferable, and silica is particularly preferable. As the inorganic filler, one of these may be used alone, or two or more of them 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, it is possible to suppress an increase in the viscosity of the varnish of the thermosetting resin, and it is possible to improve workability at the time of producing the insulating layer. The upper limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 5.0 μm or less, more preferably 2.0 μm or less, still more preferably 1.0 μm or less. As a result, phenomena such as sedimentation of the inorganic filler in the varnish of the thermosetting resin can be suppressed, and a more uniform resin film can be obtained. 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 size of the inorganic filler is measured by measuring the particle size distribution of the particles on a volume basis by, for example, a laser diffraction type particle size distribution measuring device (LA-500 manufactured by HORIBA), and the median size (D50) thereof. ) Can be the average particle size.

The inorganic filler is not particularly limited, but an inorganic filler having a monodisperse average particle size may be used, or an inorganic filler having a polydisperse average particle size may be used. Further, one kind or two or more kinds of inorganic fillers having an average particle size of monodisperse and / or polydisperse may be used in combination.

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

The lower limit of the content of the inorganic filler is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, but for example, 50% by weight or more is preferable, 55% by weight or more is more preferable. More preferably, it is 60% by weight or more. As a result, the cured product of the resin film can have particularly low thermal expansion and low water absorption. Moreover, 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, for example, 90% by weight or less, and 85% by weight or less. It may be 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 the present 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 cyanide compound with a phenol or a naphthol and, if necessary, prepolymerizing by a method such as heating. In addition, a commercially available product prepared in this manner can also be used.
By using the cyanate resin, the coefficient of linear expansion of the cured product of the resin film can be reduced. Further, the electrical characteristics (low dielectric constant, low dielectric loss tangent), mechanical strength, etc. of the cured product of the resin film can be improved.

The cyanate resin is, for example, a novolak type cyanate resin; a bisphenol type cyanate resin such as a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, a tetramethylbisphenol F type cyanate resin; a reaction between a naphthol aralkyl type phenol resin and cyanate halide. The naphthol aralkyl type cyanate resin obtained in the above; dicyclopentadiene type cyanate resin; biphenylalkyl type cyanate resin and the like can be mentioned. Among these, novolak type cyanate resin and naphthol aralkyl type cyanate resin are preferable, and novolak type cyanate resin is more preferable. By using the novolak type cyanate resin, the crosslink density of the cured product of the resin film is increased, and the heat resistance is improved.

The reason for this is that the novolak type cyanate resin forms a triazine ring after the curing reaction. Further, it is considered that the novolak 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 novolak type cyanate resin has excellent rigidity. Therefore, the heat resistance of the cured product of the resin film can be further improved.

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

The average repeating unit n of the novolak type cyanate resin represented by the general formula (I) is an arbitrary integer. The average repeating unit n is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. When the average repeating unit n is at least the above lower limit value, the heat resistance of the novolak type cyanate resin is improved, and it is possible to suppress the desorption and volatilization of the low weight substance during heating. The average repeating unit n is not particularly limited, but is preferably 10 or less, and more preferably 7 or less. When n is not more than the above upper limit value, it is possible to suppress an increase in melt viscosity and improve the moldability of the resin film.

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-xylene glycol, α, α'-dimethoxy-p-xylene, 1,4. It is obtained by condensing naphthol-aralkyl-type phenol resin obtained by reaction with −di (2-hydroxy-2-propyl) benzene or the like and cyanate halide. The repeating unit n of 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 unlikely to occur during synthesis, liquid separation property 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, R independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more and 10 or less.)

Further, one type of cyanate resin may be used alone, two or more types may be used in combination, or one type or two or more types may be used in combination with their 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, still more 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 reduce the linear expansion and increase the elastic modulus of the cured product of the resin film. On the other hand, the upper limit of the cyanate resin content 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, for example. , 20% by weight or less is more preferable. Heat resistance and moisture resistance can be improved. Further, when the content of the cyanate resin is within the above range, the storage elastic modulus E'of the cured product of the resin film can be further improved.

(Curing accelerator)
The thermosetting resin composition of the present embodiment may contain, 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, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III) Organic metal salts such as, triethylamine, tributylamine, tertiary amines such as diazabicyclo [2,2,2] octane, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, etc. Imidazoles such as 2-phenyl-4-ethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxyimidazole, etc. , Phenol compounds such as phenol, bisphenol A, nonylphenol, organic acids such as acetic acid, benzoic acid, salicylic acid, paratoluenesulfonic acid, and one or more selected from onium salt compounds. Among these, it is more preferable to contain 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 above general formula (2), P is a phosphorus atom, and R ³ , R ⁴ , R ⁵ and R ⁶ are organic groups having substituted or unsubstituted aromatic rings or heterocycles, respectively, or substituted or unsubstituted. It represents an aliphatic group and 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 or more protons that can be released to the outside of 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, 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 improved more effectively. On the other hand, the upper limit of the content of the curing accelerator may be, for example, 2.5% by weight or less, preferably 1% by weight or less, based on 100% by weight of the total solid content of the thermosetting resin composition. Good. By setting the content of the curing accelerator to the above upper limit value or less, the storage stability of the thermosetting resin composition can be improved.

(Coupling agent)
The thermosetting resin composition of the present embodiment may contain a coupling agent. The coupling agent may be added directly at the time of preparing the thermosetting resin composition, or may be added in advance to the inorganic filler. The wettability of the interface between the inorganic filler and each resin can be improved by using a coupling agent. 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 a coupling agent, the adhesion 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 a humidity environment.

Examples of the coupling agent include a silane coupling agent such as an epoxy silane coupling agent, a cationic silane coupling agent, and an aminosilane coupling agent, a titanate-based coupling agent, and a silicone oil type coupling agent. One type of coupling agent may be used alone, or two or more types may be used in combination. In the present embodiment, the coupling agent may contain a silane coupling agent.
As a result, 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 types 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 -Glysidoxypropylmethyldimethoxysilane, β- (3,4-epylcyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, γ-ureidopropyltriethoxysilane, vinyltriethoxysilane, etc. Of these, epoxy silane, mercapto silane, and amino silane are preferable, and primary amino silane or anilino silane is more preferable, and one or a combination of two or more of these can be used.

The content of the coupling agent can be appropriately adjusted with respect to the specific surface area of the inorganic filler. The lower limit of the content of such a coupling agent may be, for example, 0.01% by weight or more, preferably 0.05% by weight, 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 not more than the above upper limit value, it is possible to suppress the influence on the reaction and to suppress the decrease in the bending strength and the like of the cured product of the resin film.

(Additive)
The thermosetting resin composition of the present embodiment comprises a group consisting of dyes such as green, red, blue, yellow, and black, pigments such as black pigments, and pigments, as long as the object of the present invention is not impaired. The above components (thermosetting resin, curing agent) such as colorants, low stress agents, defoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, ion trapping agents, etc. containing one or more selected ones. , Inorganic filler, curing accelerator, coupling agent) may be included. These may be used alone or in combination of two or more.

Pigments include kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, strontium yellow, chromium hydroxide-containing, chromium oxide, cobalt aluminate, synthetic ultramarine blue and other inorganic pigments, phthalocyanine and other polycyclic pigments, and azo pigments. And so on.

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

In the present embodiment, the varnish-like thermosetting resin composition can contain a solvent.
Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellsolve, carbitol, anisole, and the like. 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 varnish-like, 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, ultrasonic dispersion method, high-pressure collision type dispersion method, high-speed rotation dispersion method, bead mill method, high-speed shear dispersion method, and rotation / revolution type dispersion method. It can be prepared by dissolving, mixing and stirring in a solvent using various mixers of.

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

The resin film of the present embodiment can be obtained by forming a varnish-like thermosetting resin composition into a film. For example, the resin film of the present embodiment can be obtained by removing a solvent from a coating film obtained by applying a varnish-like thermosetting resin composition. In such a resin film, the solvent content can be 5% by weight or less with respect to the entire resin film. In the present embodiment, the step of removing the solvent may be carried out under the conditions of, for example, 100 ° C. to 150 ° C., 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 the resin film 100 with a carrier in the present embodiment.
As shown in FIG. 1, the resin film 100 with a carrier of the present embodiment includes a carrier base material 12 and a resin film 10 made of the thermosetting resin composition provided on the carrier base material 12. Can be prepared. Thereby, the handleability of the resin film 10 can be improved.

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

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, but for example, heat resistance of polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, release papers such as polycarbonate and silicone sheets, fluororesins and polyimide resins. Examples thereof include a thermoplastic resin sheet having the above. The metal foil is not particularly limited, and is, for example, copper and \ or copper-based alloy, aluminum and \ or aluminum-based alloy, iron and \ or iron-based alloy, silver and \ or silver-based alloy, gold and gold-based alloy. , Zinc and zinc alloys, nickel and nickel alloys, tin and tin alloys and the like. Of these, a sheet made of polyethylene terephthalate is most preferable because it is inexpensive and the peel strength can be easily adjusted. As a result, it becomes easy to peel off from the resin film 100 with a carrier with an 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. As a result, 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. This makes it possible to reduce the thickness of the semiconductor device.

The thickness of the carrier base material 12 is not particularly limited, but may be, for example, 10 to 100 μm or 10 to 70 μm. This is preferable because the handleability when manufacturing the resin film 100 with a carrier is good.

The resin film 100 with a carrier of the present embodiment may be a single layer or a multilayer, and may include one type or two or more types of resin film 10. When the resin sheet has multiple layers, it may be composed of the same type or different types. Further, the resin film 100 with a carrier may have a protective film on the outermost layer side of the resin film 10.

In the present embodiment, the method for forming the carrier-attached resin film 100 is not particularly limited, but for example, a varnish-like thermosetting resin composition is applied onto the carrier base material 12 using various coater devices. A method of removing the solvent can be used by appropriately drying the coating film after forming the coating film.

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

As described above, the resin film of the present embodiment is a resin film made of the above thermosetting resin composition.
In the present embodiment, the cured product of the resin film has a microphase-separated structure in which the polymer block phase of the (meth) acrylic block copolymer is dispersed in the matrix phase obtained by curing the 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 microphase separated structure is preferably spherical, for example. This makes it possible to improve the dispersibility of the (meth) acrylic block copolymer in the cured product of the resin film containing the inorganic filler.

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. As a result, a uniform dispersed state can be maintained from the formation of the resin film to the curing process, so that it is possible to prevent the (meth) acrylic block copolymer from bleeding on the surface of the cured product of the resin film. In addition, 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, for example, 10 nm or more.

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

Further, the dispersed 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 coefficient of linear expansion of the cured product of the resin film can be lowered, so that the warpage of the obtained semiconductor package can be sufficiently suppressed.

In the present embodiment, the lower limit of the maximum bending strength of the cured product of the resin film (cured product of the thermosetting resin composition) measured by the three-point bending test is, for example, 70 MPa or more, preferably 100 MPa. The above is more preferably 120 MPa or more. As a result, the breaking strength of the cured product of the resin film can be increased. 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 cured product of the resin film measured by three-point bending test (the cured product of the thermosetting resin composition), the upper limit of the storage elastic modulus E _'25 at 25 ° C., but are not limited to, 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 of the storage elastic modulus E _'25 is not particularly limited, for example, it may be more than 1 GPa.

In the present embodiment, the lower limit 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 is, for example, 0. It is 5.5% or more, preferably 1% or more, and more preferably 2% 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, for example, 15% or less.
In the present embodiment, the bending strength and the bending elongation rate can be increased, so that a cured resin film having excellent toughness can be obtained.

The three-point bending test of the present embodiment can be performed by placing the test piece on two fulcrums arranged at a fixed distance and applying a load to one central point between the fulcrums. As an example, the varnish of the thermosetting resin composition is 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. The cured product is cut into a test piece having a length of 50 mm and a width of 10 mm. Then, in the above three-point bending test, for example, a precision universal testing machine (manufactured by Shimadzu Corporation, Autograph AG-IS) is used, the distance between two fulcrums L: 5 mm, the thickness of the test piece: 0.1 mm, and the measurement temperature. : 25 ° C., test speed: 1 mm / min. Here, 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 maximized under the above conditions, and the storage elastic modulus E'has a test force of 0.5 N to 1. It is determined by the amount of change in the bending load in the range of 0N, and the flexural modulus is a value obtained 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

Further, in the present embodiment, the lower limit of the 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. It is preferably 0.6 kN / m or more, and more preferably 0.7 kN / m or more. As a result, 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 enhanced. The upper limit of the 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, the varnish of the thermosetting resin composition is applied to a 0.2 mmt core full-surface etching product at 7 mils using an applicator, and dried at 120 ° C. for 5 minutes to obtain a core material with a resin film. obtain.
After that, YSNAP-3B (manufactured by Nippon Denki 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 / pressure pressed under the following conditions. Was carried out to obtain a substrate. (Temperature condition: The temperature is raised at a heating rate of 3 ° C./min, heated at 100 ° C. for 1 hour, then heated at a heating rate of 3 ° C./min, and heated at 200 ° C. for 1.5 hours. Conditions: 0.4 MPa).
After that, the outer layer carrier copper foil of the obtained substrate is peeled off, and an electrolytic plating film is formed on a 3 μm thick ultrathin copper foil so that the total copper thickness is 20 μm to obtain a plated substrate.
The obtained plated substrate is heat-treated at 150 ° C. for 30 minutes.
After that, the plated substrate is subjected to an etching treatment so as to leave an electrolytically plated copper film having a width of 10 mm to obtain a peel strength measurement sample.
The peel strength measurement can be performed on the peel strength measurement sample obtained as described above 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, preferably 30. % Or less, more preferably 20% or less. As a result, the copper adhesion of the cured product of the resin film can be maintained even under humidity and atmosphere conditions, so that the SAP characteristics of the obtained insulating layer can be further enhanced. The lower limit of the peel strength change rate is not particularly limited, but may be, for example, 0.1% or more.

In the present embodiment, the peel strength change rate can be measured by, for example, the following procedure. The peel strength measurement sample obtained by the 90 ° peel strength measurement was stored for 100 hours in an environment of 130 ° C. and a humidity of 85% RH. Next, the peel intensity 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 set to P _1, and is measured according to JIS C-6481: 1996 after storage. Let P _{2 be} the peel strength between the cured product and the metal foil.

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 resin film according to the present embodiment is, for example, 60 ppm / ° C. or less, preferably 55 ppm. It is / ° C. or lower, more preferably 50 ppm / ° C. or lower. As a result, the warpage of the semiconductor package can be reduced. On the other hand, the lower limit of the average coefficient of linear expansion (α1) is not particularly limited, but may be, for example, 1 ppm / ° C. or higher.

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. , Especially preferably 200 ° C. or higher. As a result, a cured product of a 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, for example, 400 ° C. or lower.
The glass transition temperature can be measured using a dynamic viscoelastic analyzer (DMA). Further, the glass transition temperature is a 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 a temperature rising rate of 5 ° C./min and a frequency of 1 Hz.

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

In the present embodiment, for example, by appropriately selecting the types and blending ratios of the components constituting the thermosetting resin composition, the maximum value of the bending strength and the storage elastic modulus of the thermosetting resin composition can be selected. E _'25, the flexural elongation, the average linear expansion coefficient can be in the desired range. Among these, for example, improving the dispersibility of the (meth) acrylic block copolymer, reducing the domain diameter of the polymer block phase, etc. are the maximum values of the bending strength and the storage elastic modulus E'. _25. Examples of factors for setting the bending elongation rate and the average linear expansion coefficient into a desired numerical range.

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

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

The cured product made of the resin film of the present embodiment may not contain a fiber base material such as a glass cloth or a paper base material. As a result, a configuration particularly suitable for forming a build-up layer (interlayer insulating layer) and a solder resist layer can be obtained.

Further, 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-layer printed wiring board. The double-sided printed wiring board is a printed wiring board in which a metal layer 303 is laminated on both sides of the insulating layer 301. The multilayer printed wiring board is a printed wiring board in which two or more build-up layers (for example, an insulating layer 305) are laminated on an insulating layer 301 which is a core layer by a plating through-hole method, a build-up method, or the like. ..

In the present embodiment, the via hole 307 may be a through hole or a non-through hole as long as it is a hole for electrically connecting the layers. The via hole 307 may be formed by burying a metal. The embedded metal may have a structure covered with an 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, for example, a metal laminated structure of the metal foil 105 and the electrolytic metal plating layer 309.
The metal layer 303 is, for example, on a surface of an insulating layer (for example, an insulating layer 301 or an insulating layer 305) made of a metal foil 105 treated with a chemical solution or a plasma treatment or a cured product of the resin film of the present embodiment. It is formed by the semi-additive process) method. For example, after applying the electrolytic metal plating film 308 on the metal foil 105 or the insulating layers 301 and 305, the non-circuit forming portion is protected by the plating resist, and the electrolytic metal plating layer 309 is attached by the electrolytic plating to obtain the plating resist. The metal layer 303 is formed by patterning the electrolytic metal plating film 309 by removal and flash etching.

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

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

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

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

Next, a modified example of the printed wiring board of this embodiment will be described. FIG. 4 is a process cross-sectional view of an example of the manufacturing process of the printed wiring board 500. FIG. 4C shows a printed wiring board 500 having no core layer.
The printed wiring board 500 of the present embodiment does not have a core layer having a fiber base material, and can be, for example, a coreless resin substrate composed of a build-up layer and a solder resist layer. It is preferable that these build-up layers and solder resist layers 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 build-up layer of the printed wiring board 500 may be a single layer or may have two or more layers.

Since the insulating layer made of the cured 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 layer 542,552,562 shown in FIG. 4C may be a circuit pattern, an electrode pad, or 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 flat surface. As a result, a plurality of semiconductor packages can be obtained by collectively encapsulating a plurality of semiconductor elements mounted on the printed wiring board 500 and then separating them into individual pieces. The printed wiring board 500 can be a panel board having a substantially circular shape or a rectangular shape.

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

Next, a modified example of the printed wiring board of this embodiment will be described. FIG. 5 is a cross-sectional view showing an example of the configuration of the printed wiring board 600.
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 utilized 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 improved more efficiently than the wafer level process.

In the present embodiment, even if the insulating layer 612 (interlayer insulating layer) and the insulating layers 630 and 632 (solder resist layer) of the coreless resin substrate 610 are composed of an insulating layer made of a cured product of the resin film of the present embodiment. Good. Since the cured resin film of the present embodiment has excellent toughness, it effectively suppresses warpage of the printed wiring board 600 and cracks of the coreless resin substrate 610 during transportation and mounting, especially during the PLP process. be able to.

Further, the printed wiring board 600 of the present embodiment has a large area on which a plurality of semiconductor elements (not shown) can be mounted in the plane thereof. Then, a plurality of semiconductor packages mounted in the in-plane direction of the printed wiring board 600 are collectively sealed, and then these are separated into individual pieces to obtain a plurality of semiconductor packages. Since the coefficient of linear expansion 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 can include a coreless resin substrate 610 and a solder resist layer (insulating layers 630, 632) formed on the surface thereof. The coreless resin substrate 610 may have a built-in semiconductor element 620. The semiconductor element 620 can be electrically connected via the via wiring 616. Further, the coreless resin substrate 610 can have at least an insulating layer 612 (interlayer insulating layer) and 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, for example, the metal layer 614 (post). In the coreless resin substrate 610, the via wiring 616 and the metal layer 614 are embedded. The surface of the metal layer 614, which is a post, may be formed in the same plane as 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 interlayer insulating layer, but is not limited to this configuration and has a structure in which a plurality of interlayer insulating layers are laminated. You may. 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 surface and the lower surface of the coreless resin substrate 610 may be covered with a solder resist layer (insulating layer 630, 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 is composed of 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 for manufacturing the printed wiring board 600 of the present embodiment is not particularly limited, but for example, the following method can be used. For example, the insulating layer 612 is formed on the support substrate. Subsequently, a via is formed in the insulating layer 612, and a metal film is embedded in the via by a plating method to form a via wiring 616. Subsequently, 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. After that, a solder resist layer (insulating layer 630, 632) is formed.
From the above, the printed wiring board 600 can be obtained.

Next, a modified example of the printed wiring board of this embodiment will be described. FIG. 6 is a cross-sectional view showing an example of the configuration of the printed wiring board 700.
The printed wiring board 700 shown in FIG. 6 can be composed of a board with a post (MIS board). For example, a substrate with a post can be composed of 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 a post may be a substrate after being individualized or a substrate having a large area before being individualized (for example, a support such as a wafer).
By using the printed wiring board 700 of the present embodiment, the productivity of the semiconductor package can be efficiently improved to the same extent as the wafer level process or more.

In the present embodiment, even if the insulating layer 712 (interlayer insulating layer) and the insulating layers 730 and 732 (solder resist layer) of the coreless resin substrate 710 are composed of an insulating layer made of a cured product of the resin film of the present embodiment. Good. Since the cured resin film of the present embodiment has excellent toughness, warpage of the printed wiring board 700 and cracks of the coreless resin substrate 710 during transportation and mounting can be effectively suppressed.

Further, the printed wiring board 700 of the present embodiment has a large area on which a plurality of semiconductor elements (not shown) can be mounted in the plane thereof. Then, a plurality of semiconductor packages mounted in the in-plane direction of the printed wiring board 700 are collectively sealed, and then these are separated into individual pieces to obtain a plurality of semiconductor packages. Since the coefficient of linear expansion of the cured product of the resin film of the present embodiment can be lowered, the package warpage can be suppressed in the obtained semiconductor package.

The printed wiring board 700 can include a coreless resin substrate 710 and solder resist layers (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 via the via wiring 716. Further, the coreless resin substrate 710 can have at least an insulating layer 712 (interlayer insulating layer), via wiring 716, and a metal layer 718 (post). The metal layer 714 (post) on the lower surface and the metal layer 718 (post) on the upper surface can be electrically connected via the via wiring 716. Further, 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. Further, the surface of the insulating layer 712 may have a polished surface. One surface of the metal layer 718 may form the same plane as the polished 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 interlayer insulating layer, but is not limited to this configuration and has a structure in which a plurality of interlayer insulating layers are laminated. You may. Via wiring 716 and metal layer 718 (post) may be formed as interlayer connection wiring 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 surface and the lower surface of the coreless resin substrate 710 may be covered with a solder resist layer (insulating layer 730, 732).

The method for manufacturing the printed wiring board 700 of the present embodiment is not particularly limited, but for example, the following method can be used. For example, a copper post (eg, metal layer 718) is formed on the insulating layer on the support substrate. The copper post is further embedded with an insulating layer. Subsequently, the surface of the copper post is exposed (that is, the copper post is cueed) by a method such as grinding or chemical etching. Subsequently, the rewiring is formed by the SAP method. By such a step, a coreless resin substrate 710 having an interlayer insulating layer can be formed. After that, by repeating the step of forming the interlayer insulating layer a plurality of times, a plurality of interlayer insulating layers having the interlayer connection wiring may be laminated. After that, a solder resist layer (insulating layer 730, 732) is formed.
From the 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 examples of the present invention, and various configurations other than the above can be adopted.
Hereinafter, an example of the reference form will be added.
1. 1. A thermosetting resin composition used for forming an insulating layer in a printed wiring board.
Thermosetting resin and
Hardener and
Inorganic filler and
Contains (meth) acrylic block copolymers,
A thermosetting resin composition having a maximum bending strength of 70 MPa or more and 1000 MPa or less in a cured product of the thermosetting resin composition measured by a three-point bending test under the following conditions.
(Three-point bending test)
The thermosetting resin composition is 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. This cured product is cut into a test piece having a length of 50 mm and a width of 10 mm. The obtained test piece is placed on two fulcrums arranged at a fixed distance, and an evaluation is performed in which a load is applied to one point in the center between the fulcrums. At this time, the conditions of the distance L between the two fulcrums: 5 mm, the thickness of the test piece: 0.1 mm, the measurement temperature: 25 ° C., and the test speed: 1 mm / min are used.
2.1. The thermosetting resin composition according to the above.
The above cured product of three-point bending the thermosetting resin composition was measured by the test, the storage modulus E _'25 at 25 ° C., or less than 1 GPa 20 GPa, a thermosetting resin composition.
3.1. Or 2. The thermosetting resin composition according to the above.
A thermosetting resin composition having a bending elongation at 25 ° C. of a cured product of the thermosetting resin composition measured by the above three-point bending test of 0.5% or more and 15% or less.
4.1. From 3. The thermosetting resin composition according to any one of the above items.
In the cured product of the thermosetting resin composition, a microphase-separated structure in which the polymer block phase of the (meth) acrylic block copolymer is dispersed in the matrix phase formed by curing the thermosetting resin. The thermosetting resin composition in which is formed.
5.4. The thermosetting resin composition according to the above.
A thermosetting resin composition having a domain diameter of 200 nm or less in the polymer block phase.
6.1. From 5. The thermosetting resin composition according to any one of the above items.
The (meth) acrylic block copolymer has 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. The block copolymer, the polymer in which the polymer block (S) and the polymer block (H) are alternately arranged, and the polymer block (S) are provided in the middle, and the polymer blocks are both ends thereof. A thermocurable resin composition containing one or more selected from triblock copolymers having (H).
7.1. From 6. The thermosetting resin composition according to any one of the above items.
A thermosetting resin composition having a number average molecular weight (Mn) of 3,000 or more and 500,000 or less of the (meth) acrylic block copolymer.
8.1. From 7. The thermosetting resin composition according to any one of the above items.
A thermosetting resin composition in which the content of the inorganic filler is 50% by weight or more and 90% by weight or less with respect to the entire thermosetting resin composition.
9.1. From 8. The thermosetting resin composition according to any one of the above items.
A thermosetting resin composition in which the inorganic filler contains silica.
10.1. To 9. The thermosetting resin composition according to any one of the above items.
A thermosetting resin composition in which the thermosetting resin contains an epoxy resin.
11.1. To 10. The thermosetting resin composition according to any one of the above items.
A thermosetting resin composition further comprising a coupling agent.
12.1. From 11. The thermosetting resin composition according to any one of the above items.
A thermosetting resin composition having an average linear expansion coefficient of 1 ppm / ° C. or higher and 60 ppm / ° C. or lower calculated in the range of 30 ° C. to 240 ° C. of the cured product of the thermosetting resin composition.
13.1. From 12. The thermosetting resin composition according to any one of the above items.
A thermosetting resin composition having a 90 ° peel strength of the cured product of the thermosetting resin composition with respect to copper foil of 0.5 kN / m or more.
14.1. To 13. The thermosetting resin composition according to any one of the above items.
A thermosetting resin composition having a glass transition temperature of a cured product of the thermosetting resin composition of 110 ° C. or higher.
15.1. From 14. The thermosetting resin composition according to any one of the above items.
The printed wiring board is a thermosetting resin composition that does not contain glass fibers.
16. Carrier base material and
1. Provided on the carrier base material. To 15. A resin film with a carrier, comprising a resin film made of the thermosetting resin composition according to any one of the above items.
17.1. To 15. A printed wiring board comprising an insulating layer composed of a cured product of the thermosetting resin composition according to any one of the above items.
18.17. With the printed wiring board described in
A semiconductor device including a semiconductor element mounted on a circuit layer of the printed wiring board or built in the printed wiring board.

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)
A varnish-like thermosetting resin composition was prepared for Examples and Comparative Examples.
First, each component was dissolved or dispersed at the solid content ratio shown in Table 1, adjusted to have a non-volatile content of 70% by weight with methyl ethyl ketone, and stirred using a high-speed stirring device to prepare a resin varnish.
The numerical value indicating the blending ratio of each component in Table 1 indicates the blending ratio (% by weight) of each component with respect to the total solid content of the thermosetting resin composition.
The details of the raw materials of 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 type epoxy resin (manufactured by 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 (manufactured by DIC Corporation, HP-5000)
(Hardener)
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), manufactured by Nippon Kayaku Co., Ltd., SB-AA)
Hardener 1: DDS (4,5'-diaminodiphenyl sulfone, manufactured by Mitsui Kagaku Fine Co., Ltd., 4,4'-DAS)
Hardener 2: Dicyandiamide (manufactured by Mitsubishi Chemical Corporation, DIZY7)
First curing agent 3: Phenolic curing agent (manufactured by Nippon Kayaku Co., Ltd., GPH103)
First curing agent 4: Phenolic curing agent (phenol novolac resin, manufactured by Sumitomo Bakelite Co., Ltd., PR-HF-3))
(Inorganic filler)
Inorganic filler 1: Silica particles (manufactured by Admatex, SC4050, average particle size 1.1 μm)
((Meta) acrylic block copolymer)
(Meta) 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 Alchema, Nanostrength M52)
(Meta) Acrylic block copolymer 2: (Acrylic monomer block copolymer (PMMA-b-PBA-b-PMMA; b = block), number average molecular weight: about 15,000, manufactured by Alchema, Nanostrength M52N)
(Curing accelerator)
Curing Accelerator 1: 2-Phenylimidazole (2PZ-PW, manufactured by Shikoku Chemicals Corporation)
(Coupling agent)
Coupling agent 1: Silane coupling agent (N-phenylγ-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573)

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

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

In the examples and comparative examples, the resin plate, the core material, and the semiconductor package were evaluated as follows. The evaluation results are shown in Table 2.

(Cured product)
A resin sheet having a thickness of 100 μm was prepared by laminating four sheets obtained by peeling a PET film as a carrier base material from the obtained resin film with a carrier. Next, the resin sheet was heat-treated at 200 ° C. for 2 hours to obtain a cured product of a thermosetting resin composition.

(Domain diameter of polymer block layer)
The obtained cured product was thinned by a microtome, and then the domain diameter was calculated by image analysis of the stained sample with a transmission electron microscope.
No bleeding 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 fixed distance, and a load was applied to one point in the center between the fulcrums. At this time, using a precision universal testing machine (manufactured by Shimadzu Corporation, Autograph AG-IS), the distance between the two fulcrums L: 5 mm, the thickness of the test piece: 0.1 mm, the measurement temperature: 25 ° C., the test speed: 1 mm. The / minute condition 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 maximized under the above conditions, and the storage elastic modulus E'is in the range of 0.5N to 1.0N in the test force. The flexural modulus was determined by the amount of change in the bending load in the above formula. Elongation rate (%): (Equation) 600 x (Deflection amount (displacement) until the test piece breaks) x (Test piece thickness) / (Distance between fulcrums) ²

(Average coefficient of linear expansion (30 ° C to 240 ° C))
A 4 mm × 40 mm test piece was cut out from the obtained cured product, and the test piece was subjected to a temperature range of 30 to 260 ° C. and a heating rate using a thermomechanical analyzer TMA (manufactured by TA Instruments, Q400). Thermomechanical analysis (TMA) was measured for 2 cycles under the conditions of 10 ° C./min, a load of 10 g, and a tension mode. The average value of the coefficient of linear expansion in the plane direction (XY direction) in the range of 30 ° C. to 240 ° C. was calculated. The coefficient of linear expansion adopted the value of the second cycle.

(Peel strength)
First, the obtained resin varnish was applied to a 0.2 mmt core fully etched product at 7 mils using an applicator, and dried at 120 ° C. for 5 minutes to obtain a core material with a resin film.
After that, YSNAP-3B (manufactured by Nippon Denki 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 / pressure pressed under the following conditions. Was carried out to obtain a substrate. (Temperature condition: The temperature was raised at a heating rate of 3 ° C./min, heated at 100 ° C. for 1 hour, then raised at a heating rate of 3 ° C./min, and heated at 200 ° C. for 1.5 hours. Conditions: 0.4 MPa).
After that, the outer layer carrier copper foil of the obtained substrate was peeled off, and an electrolytic plating film was formed on a 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.
After that, the plated substrate was subjected to an etching treatment so as to leave an electrolytically plated copper film having a width of 10 mm, and a peel strength measurement sample was obtained.
The peel strength measurement sample obtained as described 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 for 100 hours in an environment of 130 ° C. and a humidity of 85% RH. Next, the rate of change in peel strength 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 set to P _1, and is measured 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 the test piece was subjected to dynamic viscoelasticity measurement at a heating rate of 5 ° C./min and a frequency of 1 Hz. The glass transition temperature was measured by a dynamic viscoelasticity measurement (DMA device, manufactured by TA Instruments, Q800). Here, the glass transition temperature was set to the temperature at which the loss tangent tan δ shows the maximum value in the region of 100 ° C. or higher.

(Panel warp)
A 12 μm copper foil is placed on a support substrate of 250 mm in length × 250 mm in width, and the resin film with a carrier film obtained in Examples and Comparative Examples is used as a two-stage vacuum pressurizing laminator device (manufactured by Meiki Co., Ltd.). Using MVLP-500), depressurize for 30 seconds at 10 hPa or less, temperature 120 ° C., pressure 0.8 MPa, 30 seconds as 1-stage condition, temperature 120 ° C., pressure 1.0 MPa, 60 with SUS end plate as 2-stage condition. Vacuum heating and pressure molding was performed in seconds. Next, the carrier base material was peeled off from the resin film with a carrier, and then cured at 180 ° C. for 2 hours. This was repeated 3 times to form a three-layer build-up layer, and the panel warp when the SUS was peeled off 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)
×: 50 mm or more

(Handling)
After peeling the SUS, another 12 μm copper foil is etched. After that, the presence or absence of cracks in the panel was evaluated.
○: No crack ×: With crack

(Interlayer insulation reliability)
First, a roughening treatment (CZ treatment, 1 μm) was carried out 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., insulation layer thickness 0.2 mm).
Then, the obtained resin varnish was coated with an applicator at 5 mils and dried at 120 ° C. for 5 minutes to obtain a core material with a resin film.
Then, a 12 μm thick copper foil was set on the resin surface of the produced core material with a resin film, and a vacuum / pressure press was performed under the following conditions to obtain a substrate. (Temperature condition: The temperature was raised at a heating rate of 3 ° C./min, heated at 100 ° C. for 1 hour, then raised at a heating 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 etched to leave 10 mmΦ of copper, and a test sample was obtained.
Using this test sample, the continuous wet insulation resistance was evaluated under the conditions of a temperature of 130 ° C., a humidity of 85%, and an applied voltage of 3.3 V. Incidentally, it was a failure less resistance 10 ⁶ Omega. The evaluation criteria are as follows.
〇: 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 in more detail based on the above examples, these are examples of the present invention, and various configurations other than the above can be adopted.

10 Resin film 12 Carrier base material 100 Carrier-attached resin film 105 Metal foil 300 Printed wiring board 301 Insulation layer 303 Metal layer 305 Insulation layer 307 Via hole 308 Electrolytic metal plating film 309 Electrolytic metal plating layer 400 Semiconductor device 401 Insulation layer 407 Semiconductor element 410 Solder bump 413 Encapsulant layer 500 Printed wiring board 510 Support board 520 Carrier foil 530 Metal foil 540 Insulation layer 542 Metal layer 550 Insulation layer 552 Metal layer 560 Insulation layer 562 Metal layer 600 Printed wiring board 610 Coreless resin board 612 Insulation layer 614 Metal layer 616 Via wiring 618 Metal layer 620 Semiconductor element 630 Insulation layer 632 Insulation layer 640 Metal layer 650 Metal layer 652 First metal layer 654 Second metal layer 700 Printed wiring board 710 Coreless resin board 712 Insulation layer 714 Metal layer 716 Via Wiring 718 Metal layer 720 Semiconductor element 730 Insulation layer 732 Insulation layer 740 Metal layer

Claims (17)

A thermosetting resin composition used for forming an insulating layer in a printed wiring board.
Thermosetting resin and
Hardener and
Inorganic filler and
Contains (meth) acrylic block copolymers,
The thermosetting resin composition is a microphase in which the polymer block phase of the (meth) acrylic block copolymer is dispersed in a matrix phase obtained by curing the thermosetting resin in the cured product. A separated structure is formed,
A thermosetting resin composition having a maximum bending strength of 70 MPa or more and 1000 MPa or less in a cured product of the thermosetting resin composition measured by a three-point bending test under the following conditions.
(Three-point bending test)
The thermosetting resin composition is 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. This cured product is cut into a test piece having a length of 50 mm and a width of 10 mm. The obtained test piece is placed on two fulcrums arranged at a fixed distance, and an evaluation is performed in which a load is applied to one point in the center between the fulcrums. At this time, the conditions of the distance L between the two fulcrums: 5 mm, the thickness of the test piece: 0.1 mm, the measurement temperature: 25 ° C., and the test speed: 1 mm / min are used. The thermosetting resin composition according to claim 1 , wherein the cured product has a domain diameter of 200 nm or less in the polymer block phase. The thermosetting resin composition according to claim 1 or 2 .
The cured product of the previous SL three-point bending the thermosetting resin composition was measured by the test, 25 ° C. storage elastic modulus E _'25 at is less than 1 GPa 20 GPa, a thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 3 .
The cured product of the previous SL three-point bending the thermosetting resin composition was measured by the test, the flexural elongation at 25 ° C., 15% or less than 0.5%, the thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 4 .
The (meth) acrylic block copolymer has 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. The block copolymer, the polymer in which the polymer block (S) and the polymer block (H) are alternately arranged, and the polymer block (S) are provided in the middle, and the polymer blocks are both ends thereof. A thermocurable resin composition containing one or more selected from triblock copolymers having (H). The thermosetting resin composition according to any one of claims 1 to 5 .
A thermosetting resin composition having a number average molecular weight (Mn) of 3,000 or more and 500,000 or less of the (meth) acrylic block copolymer. The thermosetting resin composition according to any one of claims 1 to 6 .
A thermosetting resin composition in which the content of the inorganic filler is 50% by weight or more and 90% by weight or less with respect to the entire thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 7 .
A thermosetting resin composition in which the inorganic filler contains silica. The thermosetting resin composition according to any one of claims 1 to 8 .
A thermosetting resin composition in which 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 .
A thermosetting resin composition having an average linear expansion coefficient of 1 ppm / ° C. or higher and 60 ppm / ° C. or lower calculated in the range of 30 ° C. to 240 ° C. of the cured product of the thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 11 .
A thermosetting resin composition having a 90 ° peel strength of the cured product of the thermosetting resin composition with respect to copper foil of 0.5 kN / m or more. The thermosetting resin composition according to any one of claims 1 to 12 .
A thermosetting resin composition having a glass transition temperature of a cured product of the thermosetting resin composition 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 that does not contain glass fibers. Carrier base material and
A resin film with a carrier, comprising a resin film made of the thermosetting resin composition according to any one of claims 1 to 14 , which is provided on the carrier base material. A printed wiring board comprising an insulating layer composed of a cured product of the thermosetting resin composition according to any one of claims 1 to 14 . The printed wiring board according to claim 16 and
A semiconductor device including a semiconductor element mounted on a circuit layer of the printed wiring board or built in the printed wiring board.

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