JP6808985B2 - Resin film, resin film with carrier, printed wiring board and semiconductor device - Google Patents

Description

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

So far, resin sheets used for printed wiring boards have been developed. Examples of this type of technology include the resin sheet described in Patent Document 1. According to the same document, a resin sheet characterized by using a thermosetting component and spherical silica is described. The average linear expansion coefficient of the cured product of this resin sheet from room temperature to Tg-10 ° C. was 32 to 57 ppm / ° C. (Examples 1 to 6 in paragraph 0186).

Further, a similar technique is described in Patent Document 2. According to the same document, the coefficient of linear expansion of the cured resin sheet was 37 to 55 ppm / ° C. (Examples 1 to 11 in Tables 3 and 4).

Japanese Unexamined Patent Publication No. 2005-330401 Japanese Unexamined Patent Publication No. 2006-45388

However, in recent years, semiconductor packages are becoming thinner and thinner. As a result of examination by the present inventor based on such a development environment, it has been found that the resin sheet described in the above document has room for improvement in terms of connection reliability of the semiconductor package.

Since spherical silica is used in the resin sheet described in the above document, the coefficient of linear expansion in the plane direction (XY direction) and the coefficient of linear expansion in the thickness direction (Z direction) show almost the same value. Become. Further, in the resin sheet described in the above document, the coefficient of linear expansion in the XY direction showed a value larger than 30 ppm / ° C.
When such a conventional resin sheet is used as the interlayer insulating film of the printed wiring board, the difference in the coefficient of linear expansion in the Z direction between the interlayer insulating film and the interlayer connecting wiring becomes large, and the difference in the coefficient of linear expansion in the Z direction is large. As a result, the connection reliability in the Z direction may decrease. Here, copper is a typical example of the material for the interlayer connection wiring such as the through-hole plating layer and the via layer. The coefficient of linear expansion of copper in the Z direction is about 17 ppm.

On the other hand, from the viewpoint of reducing the warp of the semiconductor package, as a method of reducing the difference in the coefficient of linear expansion between the semiconductor chip and the printed wiring board, a method of reducing the coefficient of linear expansion of the printed wiring board in the XY direction is usually used. It is considered to be adopted.
However, in the conventional resin sheet, even if the coefficient of linear expansion in the XY direction is reduced, the coefficient of linear expansion in the Z direction is also reduced accordingly, so that the difference in the coefficient of linear expansion in the Z direction is once reduced. However, it gradually grows larger after that.

The present inventor has found such a situation, and as a result of repeated diligent studies, for example, by appropriately controlling the manufacturing conditions such as the material of the inorganic filler, the method of forming the resin film, and the method of impregnating the prepreg, the printed wiring is printed. It has been found that in a resin film made of a thermosetting resin composition used for forming an insulating layer in a substrate, the coefficient of linear expansion in the XY direction and the coefficient of linear expansion in the Z direction can be controlled separately. Regarding the anisotropic controllability of such a linear expansion integer, the thickness direction with respect to the average linear expansion coefficient (α1) in the plane direction (XY direction) calculated in the range of 50 ° C. to 150 ° C. of the cured product of the resin film. It was found that the coefficient of linear expansion ratio of the average coefficient of linear expansion (α _Z 1) in the (Z direction) can be used as an index for evaluation.
By using this index, it is possible to reduce the difference in the coefficient of linear expansion in the Z direction while reducing the coefficient of linear expansion in the XY direction, and improve the connection reliability of the thinned semiconductor package. We found what we could do and came to complete the present invention.

According to the present invention
A resin film made of a thermosetting resin composition used for forming an insulating layer in a printed wiring board.
The thermosetting resin composition contains a thermosetting resin, a curing agent, and an inorganic filler.
The inorganic filler contains an anisotropically shaped first inorganic filler and a spherical or amorphous second inorganic filler.
The anisotropically shaped first inorganic filler has a plate shape or a needle shape, and has a plate shape or a needle shape.
The aspect ratio of the anisotropically shaped first inorganic filler is 2 or more and 100 or less.
The first inorganic filler of the anisotropic shape comprises at least one selected from boron nitride, and quartz textiles or Ranaru group,
The anisotropically shaped first inorganic filler is 5% by weight or more and 90% by weight or less with respect to the entire inorganic filler.
The average linear expansion coefficient (α _Z 1) in the thickness direction (Z direction) with respect to the average linear expansion coefficient (α 1) in the plane direction (XY direction) calculated in the range of 50 ° C. to 150 ° C. of the cured product of the resin film. A resin film having a ratio of) of 1.1 or more and 10 or less is provided.

Further, according to the present invention.
Carrier base material and
Provided is a resin film with a carrier provided with the resin film provided on the carrier base material.

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

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 resin film capable of improving the connection reliability of a semiconductor package, a resin film with a carrier using the resin film, 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 resin film of the present embodiment is a resin film made of a thermosetting resin composition, and is used for forming an insulating layer in a printed wiring board. Such an insulating layer can be made of a cured product of the resin film.
The average linear expansion coefficient (α1) in the thickness direction (Z direction) with respect to the average linear expansion coefficient (α1) in the plane direction (XY direction) calculated in the range of 50 ° C. to 150 ° C. of the cured product of such a resin film. The ratio of _Z 1) can be 1.1 or more and 10 or less.

First, the present inventor appropriately controls the linear expansion coefficient in the plane direction (XY direction) with respect to the mounting surface on which the semiconductor element is mounted in the insulating layer of the printed wiring board to prevent the semiconductor package from warping. We focused on the fact that it can be reduced and the connection reliability in the XY direction can be improved.
Secondly, the present inventor makes a connection in the Z direction by reducing the difference in coefficient of linear expansion in the thickness direction (Z direction) between the insulating layer (for example, the interlayer insulating film) of the printed wiring board and the interlayer connection wiring. We focused on the ability to improve reliability.

However, since spherical silica is used in the conventional resin sheet, the coefficient of linear expansion in the plane direction (XY direction) and the coefficient of linear expansion in the thickness direction (Z direction) show almost the same value. Therefore, in the conventional resin sheet, it is difficult to control the linear expansion coefficient in the XY direction and the linear expansion coefficient in the Z direction separately, so that the above first and second conditions have not been realized at the same time. That is, even if the coefficient of linear expansion in the XY direction is reduced, the coefficient of linear expansion in the Z direction is also reduced accordingly, so that the difference in the coefficient of linear expansion in the Z direction is once small, but then gradually increases. There was a case that it became.

Based on these circumstances, as a result of diligent studies by the present inventor, for example, by appropriately controlling manufacturing conditions such as the material of the inorganic filler, the method of forming the resin film, and the method of impregnating the prepreg, the insulating layer in the printed wiring board It has been found that the coefficient of linear expansion in the XY direction and the coefficient of linear expansion in the Z direction can be controlled separately in the resin film made of the thermosetting resin composition used for forming the above. Regarding the anisotropic controllability of such a linear expansion integer, the thickness direction with respect to the average linear expansion coefficient (α1) in the plane direction (XY direction) calculated in the range of 50 ° C. to 150 ° C. of the cured product of the resin film. It was found that the coefficient of linear expansion ratio of the average coefficient of linear expansion (α _Z 1) in the (Z direction) can be used as an index for evaluation.
By using this index, it is possible to reduce the difference in the coefficient of linear expansion in the Z direction while reducing the coefficient of linear expansion in the XY direction, and improve the connection reliability of the thinned semiconductor package. We found what we could do and came to complete the present invention.

In the present embodiment, examples of the interlayer connection wiring of the printed wiring board include a metal layer such as a through-hole plating layer and a via layer. For this metal layer, for example, copper is generally used. The coefficient of linear expansion of copper in the Z direction is about 17 ppm.
By using the resin film of the present embodiment for such a printed wiring substrate, when the coefficient of linear expansion in the XY direction is smaller than that of copper, the coefficient of linear expansion in the Z direction is larger than that of copper. The coefficient of linear expansion can be controlled to decrease, and when the coefficient of linear expansion in the Z direction is about the same as or smaller than that of copper, the coefficient of linear expansion in the Z direction does not follow the coefficient of linear expansion in the XY direction. It becomes possible to control in the direction of suppressing the reduction of.
Therefore, while reducing the linear expansion coefficient in the XY direction, it is possible to reduce the difference in the linear expansion coefficient in the Z direction, and the first and second above can be satisfied at the same time, resulting in a thin layer. The connection reliability of the semiconductor package in the XY and Z directions can be improved.

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 Interface Substrate) Substrates 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 insulating layer, and is used, for example, in a build-up layer, a solder resist layer, or a PLP in a printed wiring board having no core layer. It can also be used 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 a large-area printed wiring board used for collectively producing a plurality of semiconductor packages, and an interlayer insulating layer or a solder constituting the printed wiring board. It can also be suitably used for a resist layer.

Further, since the linear expansion coefficient in the plane direction (XY direction) of the cured resin film of the present embodiment can be made lower than that in the film film direction (Z direction), the warp of the obtained semiconductor package can be sufficiently reduced. Can be suppressed.

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

The thermosetting resin composition of the present embodiment contains, for example, a thermosetting resin, a curing agent, and an inorganic filler.

(Thermosetting resin)
Examples of the thermosetting resin include epoxy resins, maleimide compounds, benzoxazine compounds, cyanate resins and the like. These may be used alone or in combination of two or more.

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 fused 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 resins; Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin having biphenylene skeleton, and other phenol aralkyl type epoxy resins; naphthylene ether type epoxy resin, naphthol type epoxy resin, naphthalenediol type epoxy resin, bifunctional to tetrafunctional naphthalene type Naphthalene type epoxy resin such as 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; fluorene type epoxy Examples include resin.

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 naphthalene, anthracene, phenanthrene, tetracene, chrysen, pyrene, triphenylene, tetraphene, or other novolak type epoxy resin having a 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 is preferably 60% by weight or less, preferably 45% by weight or less, for example. 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.

The thermosetting resin composition of the present embodiment may contain a curing agent.
Examples of the curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole and 2-ethyl-4-methylimidazole. (EMI24), 2-phenyl-4-methylimidazole (2P4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-methyl-5-hydroxyimidazole (2P4MHZ), 1-benzyl-2-phenylimidazole (1B2PZ) ) And other imidazole compounds; examples thereof include 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-Phenylenediisopropylidene) dianiline, 2,2- [4- (4-aminophenoxy) phenyl] propane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3 , 3'-diethyl-5,5'-dimethyldiphenylmethane, 3,3'-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 containing aromatic acid anhydrides; polymercaptan compounds such as polysulfide, thioesters, thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; double-added types such as organic acids such as carboxylic acid-containing polyester resins. 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, for example, phenol resin-based curing agents such as novolak type phenol resin and resole type phenol resin; urea resins such as methylol group-containing urea resin; and condensation type curing agents such as melamine resin such as methylol group-containing melamine resin are also available. You may use it. These may be used alone or in combination of two or more.

Phenolic resin-based curing agents are all monomers, oligomers, and polymers having two or more phenolic hydroxyl groups in one molecule, and their molecular weight and molecular structure are not particularly limited. For example, phenol novolac resin and cresol novolac. Novorak-type phenolic resins such as resins and naphthol novolak resins; Polyfunctional phenolic resins such as triphenolmethane-type phenolic resins; Modified phenolic resins such as terpene-modified phenolic resins and dicyclopentadiene-modified phenolic resins; phenylene skeletons and / or biphenylene skeletons Phenolic aralkyl resins having a phenol aralkyl resin, phenylene and / or aralkyl-type resins such as naphthol aralkyl resins having a biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F can be mentioned. 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 15% by weight or less, more preferably 10% by weight or less, for example. , 8% 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 thermosetting resin composition of the present embodiment may contain an inorganic filler.

In the present embodiment, the inorganic filler preferably contains a first inorganic filler having an anisotropic shape that is plate-shaped or needle-shaped. As a result of the study by the present inventor, it has been found that the coefficient of linear expansion in the in-plane direction of the cured product of the resin film can be appropriately controlled by using the first inorganic filler having such an anisotropic shape. It was. Furthermore, it is possible to impart anisotropy to predetermined physical properties such as the coefficient of linear expansion and the elastic modulus with respect to the in-plane direction of the cured product of the resin film.

Such an inorganic filler can include a first inorganic filler having an anisotropic shape and a spherical or amorphous second inorganic filler. Further, as a result of the examination by the present inventor, by using the first inorganic filler having an anisotropic shape and the second inorganic filler having a spherical or amorphous shape in combination, a line in the in-plane direction of the cured product of the resin film is used. It was found that the expansion coefficient and the linear expansion coefficient in the film thickness direction can be controlled in a well-balanced manner.

In the present embodiment, examples of the first inorganic filler include glass fiber, quartz fiber, potassium titanate, titanium oxide, aluminum borate, alumina, zonolite, wollastonite, silicon nitride, carbon nitride, aluminum nitride, and carbon dioxide. Silicon, zinc borate, titanium borate, zinc oxide, magnesium sulfate, magnesia, mulite, graphite, carbon nanotubes, carbon fibers, boron nitride, talc, calcined talc, clay, calcined clay, mica, synthetic mica, kaolin, glass, Examples thereof include boermite, silica, barium titanate, strontium titanate, calcium carbonate, calcium sulfate, barium sulfate, sodium borate, aluminum hydroxide, magnesium hydroxide, and calcium hydroxide. These may be used alone or in combination of two or more.

In the present embodiment, the anisotropically shaped first inorganic filler preferably contains one or more selected from the group consisting of boron nitride, quartz fiber, calcined talc, and glass fiber. Thereby, the coefficient of linear expansion in the in-plane direction of the cured product of the obtained resin film can be sufficiently reduced. In addition, the elastic modulus of the cured product of the resin film can be improved.

The lower limit of the aspect ratio of the first inorganic filler is not particularly limited, but may be, for example, 2 or more, 3 or more, or 5 or more. This makes it possible to impart anisotropy to a predetermined physical property with respect to the in-plane direction of the cured product of the resin film. On the other hand, the upper limit of the aspect ratio of the first inorganic filler is not particularly limited, but may be, for example, 100 or less, 80 or less, or 50 or less. As a result, the compatibility can be enhanced, so that a resin film having excellent film forming property can be obtained. In addition, the laser via workability for the cured product of the resin film can be improved.
The aspect ratio in the case of a plate is represented by the maximum diameter / thickness. The aspect ratio in the case of a needle shape is expressed by fiber length / fiber width.

The lower limit of the average diameter of the first inorganic filler is not particularly limited, but may be, for example, 0.1 μm or more, 0.5 μm or more, or 1 μm or more. As a result, the coefficient of linear expansion of the cured product of the resin film can be reduced. In addition, the mechanical strength of the cured product of the resin film can be increased. On the other hand, the upper limit of the average diameter of the first inorganic filler is not particularly limited, but may be, for example, 200 μm or less, 100 μm or less, or 50 μm or less. As a result, the insulation reliability of the cured product of the resin film can be improved.
The average diameter in the case of a plate is represented by a median diameter (average particle diameter). The average diameter in the case of a needle shape is represented by the average fiber length.

In the present embodiment, the aspect ratio and the average diameter may be calculated from a cross-sectional view obtained by an electron microscope.

Examples of the spherical or amorphous secondary inorganic filler include silica, alumina, glass, carbon, barium sulfate, calcium carbonate, zinc oxide, titanium oxide, antimony oxide, indium oxide, tin oxide, iron oxide, and aluminum borate. , Carbon black, barium titanate, strontium titanate, calcium carbonate, calcium sulfate, barium sulfate, sodium borate, calcium sulfite, magnesium carbonate, hydrotalite, calcium borate, barium metaborate, aluminum hydroxide, magnesium hydroxide , Calcium hydroxide, boron nitride, aluminum oxide, silicon carbide, silicon nitride and the like.

The lower limit of the average particle size of the spherical or amorphous second inorganic filler is not particularly limited, but is preferably 0.01 μm or more, and more preferably 0.05 μm or more. When the average particle size of the spherical or amorphous second inorganic filler is at least the above lower limit value, it is possible to suppress the increase in the viscosity of the varnish and improve the workability at the time of producing the resin film. The upper limit of the average particle size of the spherical or amorphous second 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. When the average particle size of the spherical or amorphous second inorganic filler is not more than the above upper limit, phenomena such as sedimentation of the inorganic filler in the varnish can be suppressed, and a more uniform resin layer 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.

The upper limit of the average particle size of the spherical silica is not particularly limited, but is preferably 5.0 μm or less, more preferably 4.0 μm or less, and further preferably 2.0 μm or less. Thereby, the filling property of the inorganic filler can be further improved. The lower limit of the average particle size of the spherical silica is not particularly limited, but may be, for example, 0.01 μm or more, or 0.1 μm or more.

The average particle size of the spherical or amorphous second inorganic filler is determined by measuring the particle size distribution of the particles on a volume basis with, for example, a laser diffraction type particle size distribution measuring device (LA-500 manufactured by HORIBA). D ₅₀ ) 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 or more inorganic fillers having an average particle size of monodisperse and / or polydisperse may be used in combination.

Examples of other inorganic filler materials include silicates such as talc, calcined clay, unfired clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, silica, and molten silica; calcium carbonate. , Carbonates such as magnesium carbonate, hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide; sulfates or sulfates such as barium sulfate, calcium sulfate, calcium sulfite; zinc borate, metahou Borates such as barium acid, aluminum borate, 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. For example, talc, alumina, glass, silica, mica, aluminum hydroxide or magnesium hydroxide may be used, and silica may be used among them.

The lower limit of the content of the inorganic filler (when a plurality of types are used, the total value of the contents) is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, but is, for example, 50. By weight or more is preferable, 55% by weight or more is more preferable, and 60% by weight or more is further preferable. As a result, the cured product of the resin film can have particularly low thermal expansion and low water absorption. 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.

Further, in the present embodiment, the lower limit of the content of the anisotropically shaped first inorganic filler is not particularly limited with respect to the entire inorganic filler, but is, for example, 1% by weight or more, preferably 5. It is 10% by weight or more, more preferably 10% by weight or more. As a result, the coefficient of linear expansion of the cured product of the resin film in the plane direction can be reduced, and the elastic modulus can be increased. On the other hand, the upper limit of the content of the anisotropically shaped first inorganic filler is not particularly limited with respect to the entire inorganic filler, but is, for example, 100% by weight or less, preferably 90% by weight or less. , More preferably 80% by weight or less. Thereby, the balance between the linear expansion coefficient and the elastic modulus in the plane direction of the cured product of the resin film can be appropriately controlled.

The present inventor investigated the relationship between the content of spherical silica and the coefficient of linear expansion of the cured resin in the plane direction for the cured resin containing spherical silica. As a result, it was found that the content of spherical silica and the coefficient of linear expansion in the plane direction of the cured resin show a proportional relationship and represent a function of almost linear lines.
Under these circumstances, in the conventional techniques, the content of spherical silica has been increased to a level at which the coefficient of linear expansion cannot be further reduced by spherical silica alone.

On the other hand, it was found that the coefficient of linear expansion can be effectively reduced by using an anisotropic inorganic filler such as a plate or a needle in combination with the spherical inorganic filler. That is, when compared under the same content conditions, it was found that the linear expansion coefficient in the plane direction can be reduced when the anisotropic inorganic filler is used in combination as compared with the case where the spherical inorganic filler is used alone. .. In other words, it has become possible to both reduce the coefficient of linear expansion in the XY direction and suppress the reduction in the coefficient of linear expansion in the Z direction.

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 a 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. As a result, it is possible to achieve low linear expansion and high 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. Thereby, 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.

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 heteroion.)

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, 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. 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.

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.

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.
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. , And one or a combination of two or more of these can be used. Of these, epoxysilane, mercaptosilane, and aminosilane are preferable, and primary aminosilane or anilidesilane is more preferable as the aminosilane.

The amount of the coupling agent added can be appropriately adjusted with respect to the specific surface area of the inorganic filler. The lower limit of the amount of such a coupling agent added 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 amount of the coupling agent added may be, for example, 5% by weight or less, preferably 3% by weight or less, based on 100% by weight of the total solid content of the thermosetting resin composition. When the content of the coupling agent is not more than the above upper limit value, it is possible to suppress the influence on the reaction and to suppress the decrease in the bending strength and the like of the cured product of the resin film.

The thermosetting resin composition of the present embodiment is selected from the 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, etc.) such as colorants, low stress agents, defoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, ion trapping agents, etc. Additives other than inorganic fillers, curing accelerators, coupling agents) may be included. These may be used alone or in combination of two or more.

Examples of the pigment include kaolin, titanium oxide, 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, and polycycles such as phthalocyanine. Pigments, azo pigments and the like can be mentioned.

Examples of the dye include isoindoline, isoindoline, quinophthalone, xanthene, diketopyrrolopyrrole, perylene, perylene, anthraquinone, indigoid, oxazine, quinacridone, benzimidazolone, violanthrone, 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 can include a carrier base material 12 and the resin film 10 provided on the carrier base material 12. 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. This makes it easy to peel the carrier base material 12 from the carrier-attached resin film 100 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 resin film 100 with a carrier is not particularly limited, but for example, a varnish-like thermosetting resin composition is placed on the carrier base material 12 with a comma coater, a die coater, a lip coater, and the like. A method can be used in which a coating film is formed by coating with a bar coater and then the solvent is removed by appropriately drying the coating film. Among such coating methods, a comma coater may be used from the viewpoint of productivity.
As a result of the study by the present inventor, it has been found that the planar orientation of the anisotropically shaped first inorganic filler can be controlled by using such a method. That is, by appropriately selecting the coating method, the anisotropically shaped first inorganic filler can be oriented in the plane direction (XY direction) of the resin film and the cured product of the resin film.

Further, the prepreg of the present embodiment is formed by impregnating a fiber base material such as glass fiber with a resin film. Even in such a prepreg, the orientation of the anisotropically shaped first inorganic filler can be maintained by selecting an appropriate impregnation method. For example, by preparing a resin film with a carrier, a fiber base material, and a resin film with a carrier, and performing vacuum pressing on a laminate in which these resin films are arranged toward the fiber base material, as described above. You get a prepreg.

According to the present embodiment, by adopting such a resin film or a prepreg using the resin film, it is possible to form an insulating layer in a printed wiring board in which the coefficient of linear expansion in the plane direction is reduced.

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

The upper limit of the average linear expansion coefficient (α1) in the plane direction (XY direction) calculated in the range of 50 ° C. to 150 ° C. of the cured resin film according to the present embodiment is, for example, 30 ppm / ° C. or less. It is preferably 25 ppm / ° C. or lower, more preferably 20 ppm / ° C. or lower, and even more preferably 15 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, or 2 ppm / ° C. or higher.

The upper limit of the average linear expansion coefficient (α2) in the plane direction (XY direction) calculated in the range of 150 ° C. to 250 ° C. of the cured resin film according to the present embodiment is, for example, 50 ppm / ° C. or less. It is preferably 40 ppm / ° C. or lower, more preferably 35 ppm / ° C. or lower, and even more preferably 30 ppm / ° C. or lower. As a result, it is possible to improve the warp and connection reliability of the semiconductor package when the thermal history is added (during the thermal history). On the other hand, the lower limit of the average coefficient of linear expansion (α2) is not particularly limited, but may be, for example, 1 ppm / ° C. or higher, or 2 ppm / ° C. or higher.

The plane direction calculated in the range of 150 ° C. to 250 ° C. with respect to the average linear expansion coefficient (α1) in the plane direction (XY direction) calculated in the range of 50 ° C. to 150 ° C. of the cured resin film according to the present embodiment. The linear expansion coefficient ratio of the average linear expansion coefficient (α2) in the (XY direction) is not particularly limited, but may be, for example, 1.1 or more, or 1.2 or more. This makes it possible to improve the balance between the coefficient of linear expansion at room temperature and at the time of thermal history. On the other hand, the upper limit of the linear expansion ratio is not particularly limited, but is, for example, 5 or less, preferably 4 or less, more preferably 3 or less, and further preferably 2.1 or less. As a result, the warp of the semiconductor package and the connection reliability at the time of thermal history can be sufficiently improved. In addition, the thermal characteristics of the semiconductor package can be improved.

The average linear expansion coefficient in the thickness direction (Z direction) with respect to the average linear expansion coefficient (α1) in the plane direction (XY direction) calculated in the range of 50 ° C. to 150 ° C. of the cured resin film according to the present embodiment. The lower limit of the coefficient of linear expansion ratio of (α _Z 1) is not particularly limited, but is, for example, 1.1 or more, preferably 1.2 or more, and more preferably 1.3 or more. As a result, the anisotropy of the coefficient of linear expansion in the plane direction with respect to the thickness direction can be increased. The lower limit of the coefficient of linear expansion ratio is an index for effectively lowering the coefficient of linear expansion in the plane direction. Further, since it is possible to suppress the widening of the difference in the coefficient of linear expansion from the plated metal layer in the through hole, it is possible to improve the connection reliability. On the other hand, the upper limit of the linear expansion ratio is not particularly limited, but may be, for example, 10 or less, 9 or less, or 8 or less. As a result, the balance of the coefficient of linear expansion in the thickness direction and the plane direction can be improved.

In the present embodiment, the average coefficient of linear expansion calculated in the range of 50 ° C. to 150 ° C. in the in-plane direction (XY direction) of the cured resin film obtained by heat treatment at 200 ° C. for 1 hour is defined as α ₁ . Let α ₂ be the average coefficient of linear expansion calculated in the range of 150 ° C to 250 ° C.
In the present embodiment, the average linear expansion coefficients α1 and α2 are defined by using a TMA (thermomechanical analysis) device (manufactured by TA Instruments, Q400) in a temperature range of 30 ° C. to 300 ° C. and a heating rate of 10 ° C./. It is an average value of the coefficient of linear expansion (CTE) in the plane direction (XY direction) measured under the conditions of min, a load of 10 g, and a compression mode.

In the present embodiment, the average coefficient of linear expansion calculated in the range of 50 ° C. to 150 ° C. in the thickness direction (Z direction) of the cured resin film obtained by heat treatment at 200 ° C. for 1 hour is set to αz1 and 150 ° C. The average coefficient of linear expansion calculated in the range of 250 ° C. is defined as αz2.
In the present embodiment, the average linear expansion coefficients αz1 and αz2 are defined by using a TMA (thermomechanical analysis) device (manufactured by TA Instruments, Q400) in a temperature range of 30 ° C. to 300 ° C. and a heating rate of 10 ° C./. It is an average value of the coefficient of linear expansion (CTE) in the thickness direction (Z direction) measured under the conditions of min, a load of 10 g, and a compression mode. The thickness of the measurement sample is preferably 0.5 mm or more.

In the present embodiment, the cured product of the resin film, the lower limit of the storage elastic modulus E _'30 at 30 ° C., for example, not less than 5 GPa, preferably at least 9 GPa, more preferably not less than 15 GPa. As a result, the rigidity of the cured product of the resin film can be increased. On the other hand, the cured product of the resin film, the upper limit of the storage elastic modulus E _'30 at 30 ° C., but are not limited to, for example, may be a less 40 GPa, it may be less 35 GPa. As a result, a cured product of a resin film having excellent stress relaxation ability can be realized. Further, when the above range is satisfied, the performance balance of the obtained printed wiring board in rigidity, heat resistance, and stress relaxation ability is improved, and the warpage of the printed wiring board at the time of mounting can be further reduced. As a result, in the obtained semiconductor device, the displacement of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability between the semiconductor element and the printed wiring board can be further improved.

In the present embodiment, the cured product of the resin film, the lower limit of the storage elastic modulus E _'250 at 250 ° C., for example, not less than 1 GPa, preferably not less than 1.5 GPa, more preferably 2GPa or more. This makes it possible to increase the rigidity of the cured product of the resin film during the heat history. On the other hand, the cured product of the resin film, the upper limit of the storage elastic modulus E _'250 at 250 ° C. is not particularly limited, for example, may be a less 10 GPa, it may be less 9 GPa. As a result, it is possible to realize a cured product of a resin film having excellent stress relaxation ability during thermal history. Further, when the above range is satisfied, the performance balance of the rigidity, heat resistance, and stress relaxation ability of the wiring board during thermal history is improved, and the warp of the printed wiring board during mounting can be further reduced. As a result, in the obtained semiconductor device, the displacement of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability between the semiconductor element and the printed wiring board can be further improved.

In the present embodiment, the lower limit of the glass transition temperature of the cured product of the resin film is not particularly limited, but may be, for example, 180 ° C. or higher, 200 ° C. or higher, and particularly preferably 230 ° C. or higher. 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 corresponds to the peak value of the loss tangent tan δ existing in the region of 150 ° C. or higher in the curve obtained by the dynamic viscoelasticity measurement under the conditions of the temperature rising rate of 5 ° C./min and the frequency of 1 Hz. It is the temperature to be used.

In the present embodiment, the storage elastic modulus is 200 ° C. for a cured resin film obtained by heat treatment in 1 hour, for example, using a dynamic viscoelasticity measuring device at a frequency of 1 Hz and a heating rate of 5 ° C./min. from the measurement results obtained by performing the dynamic viscoelasticity test in the conditions, it is possible to calculate the storage modulus at 30 ° C. and _{250 ℃ (E '30, E} ' 250,). 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 controlling the coating method of the thermosetting resin composition, and appropriately selecting the type and blending ratio of the components constituting the thermosetting resin composition, the thermosetting is performed. The average linear expansion coefficient (α1) of the sex resin composition in the range of 50 ° C. to 150 ° C. in the plane direction (XY direction), and the average linear expansion coefficient (α1) in the range of 150 ° C. to 250 ° C. in the plane direction (XY direction). α2), the storage elastic modulus can be within a desired range.

Among these, for example, the use of a first inorganic filler having an anisotropic shape, the formation of a coating film with a comma coater, etc. are the average lines in the plane direction (XY direction) of the heat-curable resin composition. expansion coefficient ([alpha] 1), the linear expansion coefficient of average linear expansion coefficient in the thickness direction (Z direction) (alpha _{Z 1),} with respect to the plane direction average coefficient of thermal expansion (XY direction) ([alpha] 1), the thickness direction of the (Z-direction) It can be mentioned as an element for setting the coefficient of linear expansion ratio of the average coefficient of linear expansion (α _Z 1) into a desired numerical range.

(Printed circuit board)
The printed wiring board of the present embodiment includes an insulating layer made 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 is preferably used as 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. Can be done.

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 the 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 insulation 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 the electrolytic metal plating film 308 is applied on the metal foil 105 or the insulating layers 301 and 305, the non-circuit forming portion is protected by 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, vias are formed in the insulating layer 612, and via wiring 616 in which a metal film is embedded in the vias by a plating method is formed. 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 this embodiment, the productivity of the semiconductor package can be efficiently improved to the same level as or higher than the wafer level process.

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 embodiment will be added.
1. 1. A resin film made of a thermosetting resin composition used for forming an insulating layer in a printed wiring board.
The average linear expansion coefficient (α _Z 1 ) in the thickness direction (Z direction) with respect to the average linear expansion coefficient (α 1 ) in the plane direction (XY direction) calculated in the range of 50 ° C. to 150 ° C. of the cured product of the resin film. ) Is 1.1 or more and 10 or less.
2. 2. 1. 1. The resin film described in
The plane direction (XY direction) calculated in the range of 150 ° C. to 250 ° C. with respect to the average linear expansion coefficient (α1) in the plane direction (XY direction) calculated in the range of 50 ° C. to 150 ° C. of the cured product of the resin film. A resin film having a ratio of the coefficient of linear expansion (α2) of 1.1 or more and 5 or less.
3. 3. 1. 1. Or 2. The resin film described in
The cured product of the resin film, the storage modulus E _'30 at 30 ° C. is not more than 40GPa than 5 GPa, the resin film.
4. 1. 1. From 3. The resin film described in any of
A resin film having an average linear expansion coefficient (α2) of 1 ppm / ° C. or higher and 50 ppm / ° C. or lower in the plane direction (XY direction) calculated in the range of 150 ° C. to 250 ° C. of the cured product of the resin film.
5. 1. 1. From 4. The resin film described in any of
A resin film having an average linear expansion coefficient (α1) of 1 ppm / ° C. or higher and 30 ppm / ° C. or lower in the plane direction (XY direction) calculated in the range of 50 ° C. to 150 ° C. of the cured product of the resin film.
6. 1. 1. From 5. The resin film described in any of
The thermosetting resin composition contains a thermosetting resin, a curing agent, and an inorganic filler.
A resin film in which the inorganic filler contains an anisotropically shaped first inorganic filler.
7. 6. The resin film described in
A resin film in which the anisotropically shaped first inorganic filler is plate-shaped or needle-shaped.
8. 6. Or 7. The resin film described in
A resin film in which the aspect ratio of the anisotropically shaped first inorganic filler is 2 or more and 100 or less.
9. 6. From 8. The resin film described in any of
A resin film containing a type of the anisotropically shaped first inorganic filler selected from the group consisting of boron nitride, quartz fibers, calcined talc, and glass fibers.
10. 6. To 9. The resin film described in any of
A resin film in which the inorganic filler contains a first inorganic filler having an anisotropic shape and a second inorganic filler having a spherical or amorphous shape.
11. 6. To 10. The resin film described in any of
A resin film in which the content of the first inorganic filler having an anisotropic shape is 1% by weight or more and 100% by weight or less with respect to the entire inorganic filler.
12. 6. From 11. The resin film described in any of
A resin film 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.
13. 1. 1. From 12. The resin film described in any of
The printed wiring board is a resin film that does not contain glass cloth.
14. Carrier base material and
1. Provided on the carrier base material. To 13. A resin film with a carrier, comprising the resin film according to any one of.
15. 1. 1. To 13. A printed wiring board comprising an insulating layer composed of a cured product of the resin film according to any one of.
16. 15. 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 , Reference 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 , reference examples and comparative examples, the following raw materials were used.
(Thermosetting resin)
Thermosetting resin 1: Phenolic aralkyl type epoxy resin having a biphenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., NC-3000, epoxy equivalent 275, weight average molecular weight 2000)
(Hardener)
Hardener 1: Phenolic resin-based hardener (manufactured by Nippon Kayaku Co., Ltd., KAYAHARD GPH-103, hydroxyl group equivalent 231)
(Inorganic filler)
Inorganic filler 1: Silica (spherical, manufactured by Admatex Co., Ltd., SC4050, average particle size 1.0 μm)
Inorganic filler 2: calcined talc (plate-shaped, manufactured by Fuji Tarc Industries, Ltd., FH106, average particle diameter 6 μm, aspect ratio 6)
Inorganic filler 3: Quartz fiber (needle-shaped, average diameter 4 μm, aspect ratio 20)
Inorganic filler 4: Boron nitride (plate shape, Denka Co., Ltd., GP, average particle size 8 μm, aspect ratio 8)
(Cyanate resin)
Cyanate resin 1: Cyanate resin (manufactured by Lonza Japan Co., Ltd., PT-30, weight average molecular weight 700)
(Coupling agent)
Coupling Agent 1: Epoxy Silane Coupling Agent (manufactured by GE Toshiba Silicone Co., Ltd., A-187)

(Resin film with carrier)
The obtained resin varnish was applied onto a PET film as a carrier base material using a comma coater, and then the solvent was removed under the conditions of 150 ° C. for 3 minutes to form a resin film having a thickness of 30 μm. As a result, a resin film with a carrier was obtained.

(Resin plate)
A resin sheet having a thickness of 90 μm was prepared by laminating three 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 230 ° C. for 2 hours to obtain a cured product.

(Core material)
In Examples , Reference Examples and Comparative Examples, the obtained resin varnish was applied to a copper foil as a carrier base material using a comma coater, and then the solvent was removed at 150 ° C. for 3 minutes to obtain a thickness of 30 μm. A resin film was formed. As a result, a resin film with a carrier was obtained. Subsequently, the obtained resin film with carrier, glass woven cloth (cross type # 2116, T glass, basis weight 104 g / m ² ), and resin film with carrier are laminated in this order, and the resin of the resin film with carrier is arranged. A prepreg was obtained by vacuum pressing the laminate in which the film was arranged toward the fiber substrate.
Further, the obtained prepreg was cured at 230 ° C. for 2 hours to obtain a core material (core layer).

(Manufacturing of semiconductor packages)
1. 1. Manufacture of Printed Wiring Board After roughening the surface copper foil layer of the core material obtained above 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) 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. For the circuit board after forming the circuit pattern, prepreg (manufactured by Sumitomo Bakelite Co., Ltd., LAZ-6785TT-R, insulating layer thickness 0.03 mm) and copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd.) , 3EC-M3-VLP, 12um) were laminated on both sides, and then cured by a vacuum press under the condition of 230 ° C. for 2 hours. Next, after circuit processing by the subtractive method, a solder resist (manufactured by Taiyo Ink Mfg. Co., Ltd., PSR-800 AUS SR1) was laminated on both sides and opened by photopatterning (exposure, development) to obtain a printed wiring board. It was.

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

In the examples , reference examples and comparative examples, the resin plate, the core material and the semiconductor package were evaluated as follows. The evaluation results are shown in Tables 2 and 3.

(Coefficient of linear expansion)
1. 1. Linear expansion coefficient in the XY direction Three PET films, which are carrier base materials, were peeled off from the obtained resin film with a carrier, and three sheets were laminated to prepare a resin sheet having a thickness of 90 μm. Next, the resin sheet was heat-treated at 230 ° C. for 2 hours to obtain a cured product. A 5 mm × 8 mm test piece was cut out from the obtained cured product, and the test piece was subjected to a temperature range of 30 to 300 ° 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 compression mode. The average value α _{1 of the} coefficient of linear expansion in the plane direction (XY direction) in the range of 50 ° C. to 150 ° C. and the mean value α _{2 of the} coefficient of linear expansion in the plane direction (XY direction) in the range of 150 ° C. to 250 ° C. were calculated. .. The coefficient of linear expansion adopted the value of the second cycle.
2. 2. Linear expansion coefficient in the Z direction Thirty sheets of the obtained resin film with a carrier from which the PET film as a carrier base material was peeled off were laminated to prepare a resin sheet having a thickness of 900 μm. Next, the resin sheet was heat-treated at 230 ° C. for 2 hours to obtain a cured product. A 10 mm × 10 mm test piece was cut out from the obtained cured product, and the test piece was subjected to a temperature range of 30 ° C. to 300 ° C. using a TMA (thermomechanical analysis) device (manufactured by TA Instruments, Q400). The average linear expansion coefficients αz1 and αz2 were calculated from the average values of the linear expansion coefficients (CTE) in the thickness direction (Z direction) measured under the conditions of a heating rate of 10 ° C./min, a load of 10 g, and a compression mode. The coefficient of linear expansion adopted the value of the second cycle.

(Storage modulus E')
The storage elastic modulus E'was measured by a dynamic viscoelasticity measurement (DMA device, manufactured by TA Instruments, Q800).
A resin sheet having a thickness of 90 μm was prepared by laminating three 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 230 ° C. for 2 hours to obtain a cured product. A test piece of 8 mm × 40 mm was cut out from the obtained cured product, and the test piece was measured for storage elastic modulus from 20 ° C. to 260 ° C. at a heating rate of 5 ° C./min and a frequency of 1 Hz. storage elastic modulus at 250 ° C. E was calculated _'30, E' _250.

(Evaluation of warpage of semiconductor package)
The warpage of the obtained semiconductor device at room temperature of 30 ° C. was evaluated using a temperature-variable laser coordinate measuring machine (manufactured by Hitachi Technology and Service Co., Ltd., model LS220-MT100MT50). The sample chamber of the measuring machine was installed with the semiconductor element surface facing down, the displacement in the height direction was measured, and the value with the largest displacement difference was defined as the amount of warpage. The evaluation criteria are as follows.
〇: Warp amount is less than 150 μm ×: Warp amount is 150 μm or more

In the core materials of Examples 6 and 7, the ratio of the average linear expansion coefficient (α _Z 1) in the thickness direction (Z direction) to the average linear expansion coefficient (α 1) in the plane direction (XY direction) is 1.1 or more. It was obtained by using the resin films of Examples 6 and 7, and the anisotropy of the coefficient of linear expansion in the XY direction and the coefficient of linear expansion in the Z direction is maintained. Therefore, in the core materials of Examples 6 and 7, the difference in the coefficient of linear expansion in the Z direction from that of copper (the coefficient of linear expansion in the Z direction is 17 ppm) is smaller than that in Comparative Example 1. Therefore, in Examples 6 and 7, the connection reliability in the Z direction was also good.
Therefore, by using the resin film made of the thermosetting resin composition of the example, the difference in the coefficient of linear expansion in the Z direction can be reduced while reducing the coefficient of linear expansion in the XY direction. Moreover, it was possible to realize a printed wiring board that can improve the connection reliability in the Z direction.

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 Electroless metal plating film 309 Electroless metal plating layer 311 Core layer 317 Build-up layer 400 Semiconductor Equipment 401 Solder resist layer 407 Semiconductor element 410 Solder bump 413 Encapsulant layer

Claims (10)

A resin film made of a thermosetting resin composition used for forming an insulating layer in a printed wiring board.
The thermosetting resin composition contains a thermosetting resin, a curing agent, and an inorganic filler.
The inorganic filler contains an anisotropically shaped first inorganic filler and a spherical or amorphous second inorganic filler.
The anisotropically shaped first inorganic filler has a plate shape or a needle shape, and has a plate shape or a needle shape.
The aspect ratio of the anisotropically shaped first inorganic filler is 2 or more and 100 or less.
The first inorganic filler of the anisotropic shape comprises at least one selected from boron nitride, and quartz textiles or Ranaru group,
The anisotropically shaped first inorganic filler is 5% by weight or more and 90% by weight or less with respect to the entire inorganic filler.
The average linear expansion coefficient (α _Z 1) in the thickness direction (Z direction) with respect to the average linear expansion coefficient (α 1) in the plane direction (XY direction) calculated in the range of 50 ° C. to 150 ° C. of the cured product of the resin film. ) Is 1.1 or more and 10 or less. The resin film according to claim 1.
The plane direction (XY direction) calculated in the range of 150 ° C. to 250 ° C. with respect to the average linear expansion coefficient (α1) in the plane direction (XY direction) calculated in the range of 50 ° C. to 150 ° C. of the cured product of the resin film. A resin film having a ratio of the coefficient of linear expansion (α2) of 1.1 or more and 5 or less. The resin film according to claim 1 or 2.
The cured product of the resin film, the storage modulus E _'30 at 30 ° C. is not more than 40GPa than 5 GPa, the resin film. The resin film according to any one of claims 1 to 3.
A resin film having an average linear expansion coefficient (α2) of 1 ppm / ° C. or higher and 50 ppm / ° C. or lower in the plane direction (XY direction) calculated in the range of 150 ° C. to 250 ° C. of the cured product of the resin film. The resin film according to any one of claims 1 to 4.
A resin film having an average linear expansion coefficient (α1) of 1 ppm / ° C. or higher and 30 ppm / ° C. or lower in the plane direction (XY direction) calculated in the range of 50 ° C. to 150 ° C. of the cured product of the resin film. The resin film according to any one of claims 1 to 5.
A resin film 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 resin film according to any one of claims 1 to 6.
The printed wiring board is a resin film that does not contain glass cloth. Carrier base material and
A resin film with a carrier, comprising the resin film according to any one of claims 1 to 7, which is provided on the carrier base material. A printed wiring board comprising an insulating layer made of a cured product of the resin film according to any one of claims 1 to 7. The printed wiring board according to claim 9 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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