JP2020015864A - Resin composition, sheet-like laminated material, printed wiring board, semiconductor chip package, and semiconductor device - Google Patents

Abstract

To provide a resin composition and the like capable of giving a cured product which can suppress warpage and has a low dielectric loss tangent even after being placed under high temperature and high humidity for a long time.SOLUTION: The resin composition contains (A) a glycidyl amine type epoxy resin, (B) a polyvalent glycidyl compound having an aromatic ring to which a glycidyl group and a glycidyloxy group are directly bonded respectively, (C) a curing agent, and (D) an inorganic filler. The content of the component (A) is 3-15 mass%, and the content of the component (B) is 0.2-6.5 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a sheet-like laminated material, a printed wiring board, a semiconductor chip package, and a semiconductor device.

  In recent years, demand for small high-performance electronic devices such as smartphones and tablet devices has been increasing, and accordingly, insulating materials used for these small electronic devices have been required to have higher functions. As such an insulating material, for example, a material formed by curing a resin composition is known (for example, see Patent Document 1).

JP-A-2015-127397

  In recent years, since a smaller semiconductor chip package is required, the thickness of an insulating layer and a silicon chip used for the semiconductor chip package are also required to be reduced. For this reason, development of an insulating layer capable of suppressing warping even when the thickness is small is desired. Furthermore, it is required to keep the dielectric loss tangent low even after being placed under severe conditions such as high temperature and high humidity for a long time. However, the conventional resin composition still has room for improvement in evaluation of warpage and dielectric loss tangent of the cured product.

  The present invention provides a resin composition capable of suppressing warpage and obtaining a cured product having a low dielectric loss tangent even after being placed under high temperature and high humidity for a long time; a sheet-like laminated material containing the resin composition; It is an object to provide a printed wiring board provided with an insulating layer made of a product; a semiconductor chip package including the cured product; and a semiconductor device including the cured product.

  The present inventors have conducted intensive studies on the above problems, and as a result, by including the components (A), (B), (C) and (D) in a specific content in the resin composition, They have found that the problem can be solved, and have completed the present invention.

  That is, the present invention includes the following contents.

[1] Contains (A) a glycidylamine type epoxy resin, (B) a polyvalent glycidyl compound having an aromatic ring in which a glycidyl group and a glycidyloxy group are directly bonded, (C) a curing agent, and (D) an inorganic filler. Assuming that the nonvolatile component in the resin composition is 100% by mass, the content of the component (A) is 3% by mass to 15% by mass, and the nonvolatile component in the resin composition is Is 100% by mass, the content of the component (B) is from 0.2% by mass to 6.5% by mass.
[2] The resin composition according to [1], wherein the content of the component (A) is 5% by mass to 10% by mass when the nonvolatile component in the resin composition is 100% by mass.
[3] The resin composition according to [1] or [2], wherein the component (C) is selected from the group consisting of a phenol-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, and an imidazole-based curing agent. object.
[4] The resin according to any one of [1] to [3], wherein the content of the component (D) is 80% by mass or more when the nonvolatile component in the resin composition is 100% by mass. Composition.
[5] The resin composition according to any one of [1] to [4], which is used for forming an insulating layer for forming a conductor layer.
[6] The resin composition according to any one of [1] to [4], which is for sealing a semiconductor chip.
[7] A sheet-like laminated material containing the resin composition according to any one of [1] to [4].
[8] A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of [1] to [4].
[9] A semiconductor chip package comprising a cured product of the resin composition according to any one of [1] to [4].
[10] A semiconductor device comprising a cured product of the resin composition according to any one of [1] to [4].

  According to the present invention, a resin composition capable of suppressing warpage and obtaining a cured product having a low dielectric loss tangent even after being placed under a high temperature and high humidity for a long time; a sheet-like laminated material containing the resin composition; A printed wiring board provided with an insulating layer made of the cured product; a semiconductor chip package containing the cured product; and a semiconductor device containing the cured product.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and equivalents thereof.

<Resin composition>
The resin composition of the present invention comprises (A) a glycidylamine-type epoxy resin, (B) a polyvalent glycidyl compound having an aromatic ring in which a glycidyl group and a glycidyloxy group are directly bonded, (C) a curing agent, and (D) When the composition contains an inorganic filler and the nonvolatile component in the resin composition is 100% by mass, the content of the component (A) is 3% by mass to 15% by mass, and the content of the component (B) is It is 0.2% by mass to 6.5% by mass.

  By using such a resin composition, the desired effect of the present invention is obtained in that warpage can be suppressed and a cured product having a low dielectric loss tangent can be obtained even after being placed under high temperature and high humidity for a long time.

  The resin composition of the present invention may further contain optional components in addition to the components (A), (B), (C), and (D). Optional components include, for example, (E) other epoxy resins, and (F) other additives. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Glycidylamine type epoxy resin>
The resin composition according to the present invention contains (A) a glycidylamine type epoxy resin. (A) The glycidylamine type epoxy resin refers to an epoxy resin having at least one glycidylamino group and / or diglycidylamino group. The glycidylamino group includes one epoxy group, and the diglycidylamino group includes two epoxy groups.

  (A) The glycidylamine type epoxy resin is preferably a bifunctional or more glycidylamine type epoxy resin having two or more epoxy groups in one molecule, from the viewpoint of obtaining a cured product having excellent heat resistance. More preferably, it is a bifunctional or trifunctional glycidylamine type epoxy resin having two or three epoxy groups in the molecule. Here, the epoxy group is not limited to those derived from a glycidylamino group and a diglycidylamino group, and may include those derived from a glycidyloxy group. When the nonvolatile component of the glycidylamine-type epoxy resin is 100% by mass, the proportion of the bifunctional or higher-functional glycidylamine-type epoxy resin is preferably 50% by mass or more, more preferably 60%, from the viewpoint of increasing the heat resistance of the cured product. % By mass or more, more preferably 70% by mass or more.

  The component (A) preferably has one or more aromatic rings in the molecule from the viewpoint of further improving heat resistance and lowering the coefficient of linear thermal expansion. In the present specification, the aromatic ring refers to an aromatic carbon ring such as a benzene ring or a naphthalene ring, or an aromatic heterocyclic ring such as a pyridine ring, a pyrrole ring, a furan ring, or a thiophene ring. When the molecule has two or more aromatic rings, the aromatic rings may be directly bonded to each other or may be bonded via an oxygen atom, an alkylene group, a combination thereof, or the like.

  In the present specification, the alkylene group refers to a linear or branched divalent aliphatic saturated hydrocarbon group. An alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 5 carbon atoms is more preferable. For example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a 1,1-dimethylethylene group, and the like are mentioned, and the bonding positions thereof are not particularly limited.

  In the component (A), a glycidylamino group and a diglycidylamino group can be directly bonded to an aromatic ring. The aromatic ring may have another substituent in addition to the glycidylamino group and the diglycidylamino group. Here, examples of the other substituent include a monovalent epoxy-containing group and a monovalent hydrocarbon group. Examples of the monovalent epoxy-containing group include a glycidyloxy group. Examples of the monovalent hydrocarbon group include an alkyl group and an aryl group.

  In the present specification, the alkyl group refers to a linear or branched monovalent aliphatic saturated hydrocarbon group. An alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl and the like.

  In the present specification, an aryl group refers to a monovalent aromatic hydrocarbon group. An aryl group having 6 to 14 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. For example, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, 2-anthryl and the like can be mentioned.

  As the component (A), one type may be used alone, or two or more types may be used in combination.

  Preferred examples of the component (A) from the viewpoint of significantly obtaining the desired effects of the present invention include those represented by the following formula (A-1).

  In the formula (A-1), n independently represents an integer of 0 to 4. Among them, n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. In the formula (A-1), m represents an integer of 1 to 3. Among them, m is preferably 1 or 2, and more preferably 1.

In the formula (A-1), R ¹¹ independently represents a monovalent epoxy-containing group such as a glycidyloxy group and a monovalent hydrocarbon group such as an alkyl group and an aryl group. When R ¹¹ is a glycidyloxy group, it is preferable that R ¹¹ is bonded to the para position based on the bonding site between the nitrogen atom and the benzene ring. When R ¹¹ is an alkyl group, R ¹¹ is preferably bonded to the ortho-position based on the bonding site between the nitrogen atom and the benzene ring.

In Formula (A-1), R ¹² represents a hydrogen atom or a monovalent to trivalent hydrocarbon group. Examples of the divalent hydrocarbon group include an alkylene group and an arylene group. When m is 1, from the viewpoint of obtaining the desired effect of the present invention, R ¹² is preferably an alkyl group, and more preferably a methyl group. When m is 2, R ¹² is preferably an alkylene group, and more preferably a methylene group, from the viewpoint of obtaining the desired effects of the present invention.

  In the present specification, an arylene group refers to a divalent aromatic hydrocarbon group. An arylene group having 6 to 14 carbon atoms is preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. For example, a phenylene group, a naphthylene group, a biphenylene group and the like can be mentioned, and their bonding positions are not particularly limited.

  Specific examples of the component (A) include “630” and “630LSD” manufactured by Mitsubishi Chemical Corporation (as in the following formula (A-2)), and “EP3980S” manufactured by ADEKA (in the following formula (A-3)). Street), "EP3950S", "EP3950L", "ELM-100", "ELM-100H", "ELM-434", "ELM-434L" manufactured by Sumitomo Chemical Co., Ltd., and the like. These may be used alone or in combination of two or more.

  (A) The epoxy equivalent of the glycidylamine type epoxy resin is preferably 50 to 5000 g / eq, more preferably 50 to 3000 g / eq, still more preferably 60 to 2000 g / eq, and particularly preferably 70 to 1000 g / eq. When the epoxy equivalent of the glycidylamine type epoxy resin is within the above range, the crosslinked density of the cured product of the resin composition becomes sufficient, and an insulating layer having a small surface roughness can be obtained.

  (A) The weight average molecular weight (Mw) of the glycidylamine type epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, and still more preferably from 400 to 1500.

  When the nonvolatile component in the resin composition is 100% by mass, the content of the component (A) in the resin composition is 3% by mass to 15% by mass. The content of the component (A) is preferably 4% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more, from the viewpoint of suppressing the warpage of the cured product. The upper limit is preferably 12% by mass or less, more preferably 10% by mass or less, and still more preferably 8% by mass or less, from the viewpoint of suppressing the dielectric loss tangent of the cured product after a high temperature and high humidity environment test (HAST).

<(B) a polyvalent glycidyl compound having an aromatic ring in which a glycidyl group and a glycidyloxy group are directly bonded>
The resin composition according to the present invention contains (B) a polyvalent glycidyl compound. (B) The polyvalent glycidyl compound has at least one aromatic ring, and at least one glycidyl group and at least one glycidyloxy group are directly bonded to the same aromatic ring. When the molecule has two or more aromatic rings, the aromatic rings may be directly bonded to each other or may be bonded via an oxygen atom, an alkylene group, a combination thereof, or the like. The aromatic ring may have another substituent in addition to the glycidyl group and the glycidyloxy group. Here, examples of the other substituent include a monovalent hydrocarbon group.

  As the component (B), one type may be used alone, or two or more types may be used in combination.

  Preferred examples of the component (B) from the viewpoint of obtaining the desired effects of the present invention significantly include those represented by the following formula (B-1).

  In formula (B-1), the definitions and preferred ranges of n 'and m' are the same as those of n and m in formula (A-1), respectively.

In the formula (B-1), R ²¹ independently represents a monovalent hydrocarbon group such as an alkyl group and an aryl group.

In the formula (B-1), R ²² represents a hydrogen atom or a monovalent to trivalent hydrocarbon group. When m ′ is 1, R ²² is preferably an alkyl group, and more preferably a methyl group, from the viewpoint of obtaining the desired effects of the present invention. When m ′ is 2, R ²² is preferably an alkylene group, and more preferably a dimethylmethylene group, from the viewpoint of obtaining the desired effects of the present invention.

  Specific examples of the component (B) include “BATG” (shown by the following formula (B-2)) manufactured by Showa Denko KK

  (B) The polyvalent glycidyl compound preferably has an epoxy equivalent of 50 to 5000 g / eq, more preferably 50 to 3000 g / eq, still more preferably 60 to 2000 g / eq, and particularly preferably 70 to 1000 g / eq. When the epoxy equivalent of the polyvalent glycidyl compound is in the above range, the crosslinked density of the cured product of the resin composition becomes sufficient, and an insulating layer with small surface roughness can be obtained.

  (B) The molecular weight of the polyvalent glycidyl compound is preferably from 100 to 5,000, more preferably from 150 to 3,000, and still more preferably from 200 to 1500.

  When the nonvolatile component in the resin composition is 100% by mass, the content of the component (B) in the resin composition is from 0.2% by mass to 6.5% by mass. The content of the component (B) is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and still more preferably 1% by mass or more, from the viewpoint of suppressing the warpage of the cured product. The upper limit is preferably 6% by mass or less, more preferably 5% by mass or less, and even more preferably 4% by mass or less, from the viewpoint of suppressing the dielectric loss tangent of the cured product after HAST.

<(C) curing agent>
The resin composition according to the present invention contains (C) a curing agent.

  (C) The curing agent is not particularly limited as long as it has a function of curing an epoxy resin, and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an acid anhydride-based curing agent, an active ester-based curing agent, and a benzoxazine-based curing agent. Examples of the curing agent include a curing agent, a cyanate ester-based curing agent, a carbodiimide-based curing agent, a phosphorus-based curing agent, an amine-based curing agent, an imidazole-based curing agent, a guanidine-based curing agent, and a metal-based curing agent. Among them, from the viewpoint of obtaining a better desired effect of the present invention, a phenol-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, and a curing agent selected from the group consisting of imidazole-based curing agents. preferable. (C) The curing agent may be used alone or in combination of two or more.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. Among them, a phenol novolak resin containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7851”, “MEH-8000H” manufactured by Meiwa Kasei Co., Ltd., Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-180", "SN-495", "SN-375", "SN-395", DIC "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA" -1356 "and" TD2090 ".

  Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic acid Anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride Melitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hex Hydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione, ethylene glycol bis (anhydrotrimellitate), methylbicyclo [2. 2.1] Heptane-2,3-dicarboxylic anhydride / bicyclo [2.2.1] Heptane-2,3-dicarboxylic anhydride (“HNA-100” manufactured by Nippon Rika Co., Ltd. as a commercial product) And polymer type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized.

  The active ester-based curing agent is not particularly limited, but generally has a highly reactive ester group such as a phenol ester, a thiophenol ester, an N-hydroxyamine ester, or an ester of a heterocyclic hydroxy compound in one molecule. Are preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples include benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolak, and the like. Here, the “dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Specifically, an active ester compound containing a dicyclopentadiene diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated phenol novolak, and an active ester compound containing a benzoylated phenol novolak are preferable. Among them, an active ester compound having a naphthalene structure and an active ester compound having a dicyclopentadiene-type diphenol structure are more preferable. The “dicyclopentadiene-type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

  Commercially available active ester curing agents include, as active ester compounds having a dicyclopentadiene-type diphenol structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000”, “HPC-8000H”, “ “HPC-8000-65T”, “HPC-8000H-65TM”, “EXB-8000L”, “EXB-8000L-65TM” (manufactured by DIC); “EXB9416-70BK”, “EXB” as active ester compounds containing a naphthalene structure -8150-65T "(manufactured by DIC);" DC808 "(manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolak;" YLH1026 "(manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolak "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent which is an acetylated product of phenol novolak; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent which is a benzoylated product of phenol novolak. "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and the like.

  Specific examples of the benzoxazine-based curing agent include “JBZ-OP100D” and “ODA-BOZ” manufactured by JFE Chemical Company; “HFB2006M” manufactured by Showa Kogyo Co., Ltd .; and “Pd” manufactured by Shikoku Chemical Industry Co., Ltd. "Fa" and the like.

  Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5- Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Phenol novolak and Polyfunctional cyanate resin derived from resol novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester-based curing agent include “PT30” and “PT60” (all are phenol novolac-type polyfunctional cyanate ester resins), “BA230” and “BA230S75” (part of bisphenol A dicyanate) manufactured by Lonza Japan. Or a prepolymer in which all are triazined to form a trimer).

  Specific examples of the carbodiimide-based curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical.

  Examples of the phosphorus-based curing agent include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like can be mentioned.

  Examples of the amine-based curing agent include triethylamine, tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5, Aliphatic amine-based curing agents such as 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene; benzidine, o-tolidine, 4,4 ′ -Diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane (a commercially available product, "Kayabond C-100" manufactured by Nippon Kayaku), 4,4'-diamino-3,3'-diethyldiphenylmethane ("Kayahard A-A" manufactured by Nippon Kayaku as a commercial product) 4,4'-Diamino-3,3 ', 5,5 -Tetramethyldiphenylmethane (a commercially available product “Kayabond C-200S” manufactured by Nippon Kayaku), 4,4′-diamino-3,3 ′, 5,5′-tetraethyldiphenylmethane (a commercially available product manufactured by Nippon Kayaku "Kayabond C-300S"), 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diaminodiphenylether, 1,3-bis (3-aminophenoxy) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-amino Phenoxy) neopentane, 4,4 '-[1,3-phenylenebis (1-methyl-ethylidene)] bisaniline (commercially available from Mitsui Chemicals, Inc.) Bisaniline M "), 4,4 '-[1,4-phenylenebis (1-methyl-ethylidene)] bisaniline (a commercially available product," bisaniline P "manufactured by Mitsui Chemicals, Inc.), 2,2-bis [4- ( 4-Aminophenoxy) phenyl] propane (commercially available product “BAPP” manufactured by Wakayama Seika), 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4′-bis ( Aromatic amine-based curing agents such as 4-aminophenoxy) biphenyl are exemplified.

  Examples of the imidazole-based curing agent include, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, -Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2 − Nylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-Ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl- - benzyl imidazolium chloride, 2-methyl-imidazoline, adduct of 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compound and an epoxy resin.

  As the imidazole-based curing agent, a commercially available product may be used, for example, “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine-based curing agent include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and tetramethylguanidine. Methylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca -5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1- Allyl biguanide, 1-phenyl biguanide, 1- (o- Lil) biguanides, and the like.

  Examples of the metal-based curing agent include an organic metal complex or an organic metal salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. And the like, an organic iron complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

  When a curing agent is included, the ratio of the epoxy resin to the curing agent is 1: 0.2 to 1: in the ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent]. The range of 2 is preferable, 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1.2 is further preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and differs depending on the type of the curing agent. Further, the total number of epoxy groups of the epoxy resin is a value obtained by summing the value obtained by dividing the nonvolatile component mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent, It is a value obtained by dividing the value obtained by dividing the mass of the non-volatile component of each curing agent by the equivalent of the reactive group for all curing agents. By setting the ratio of the epoxy resin to the curing agent in such a range, the heat resistance of the obtained cured product is further improved.

  When the nonvolatile component in the resin composition is 100% by mass, the content of the component (C) in the resin composition is preferably 0.1% by mass or more from the viewpoint of obtaining the desired effect of the present invention. It is preferably at least 0.5% by mass, more preferably at least 1% by mass. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 7% by mass or less, from the viewpoint of obtaining the desired effects of the present invention.

<(D) Inorganic filler>
The resin composition according to the present invention contains (D) an inorganic filler.

  (D) The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate , Titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphate tungstate. It is suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As the silica, spherical silica is preferable. (D) The inorganic filler may be used singly or in combination of two or more.

  (D) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Chemical Industry Co., Ltd .; "SP60-05", "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-" manufactured by Tokuyama Corporation 5N ";" SC2500SQ "," SO-C4 "," SO-C2 "," SO-C1 ";

  (D) The average particle size of the inorganic filler is not particularly limited, but is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, from the viewpoint of obtaining the desired effects of the present invention. It is more preferably at most 6 μm, particularly preferably at most 5 μm. The lower limit of the average particle size of the inorganic filler is preferably 0.1 μm or more, more preferably 1 μm or more, further preferably 2 μm or more, still more preferably 3 μm or more, particularly preferably from the viewpoint of obtaining the desired effect of the present invention. Is 4 μm or more. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter can be measured by setting the median diameter as the average particle diameter. As the measurement sample, a sample in which 100 mg of an inorganic filler and 10 g of methyl ethyl ketone are weighed in a vial and dispersed with ultrasonic waves for 10 minutes can be used. The measurement sample, using a laser diffraction type particle size distribution measuring device, the light source wavelength used is set to blue and red, and the volume-based particle size distribution of the inorganic filler is measured by a flow cell method, and from the obtained particle size distribution, The average particle diameter was calculated as the median diameter. As the laser diffraction type particle size distribution measuring device, for example, "LA-960" manufactured by Horiba, Ltd. and the like can be mentioned.

  (D) From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, an alkoxysilane compound, an organosilazane compound, a titanate-based coupling. It is preferably treated with one or more surface treatment agents such as agents. Commercially available surface treatment agents include, for example, “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu "KBE903" (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-" manufactured by Shin-Etsu Chemical Co., Ltd. 7103 "(3,3,3-trifluoropropyltrimethoxysilane) and the like.

  The degree of the surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% by mass to 5% by mass, and is preferably surface-treated with 0.2% by mass to 3% by mass. The surface treatment is preferably performed at 0.3% by mass to 2% by mass.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferred. On the other hand, from the viewpoint of preventing an increase in the melt viscosity at the melt viscosity or sheet form a resin varnish, preferably 1 mg / ^{m 2} or less, more preferably 0.8 mg / ^{m 2} or less, 0.5 mg / ^{m 2} or less is more preferable.

  (D) The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. or the like can be used.

(D) The specific surface area of the inorganic filler is preferably 1 m ² / g or more, more preferably 2 m ² / g or more, particularly preferably 3 m ² / g or more from the viewpoint of further improving the effect of the present invention. The upper limit is not particularly limited, but is preferably 50 m ² / g or less, more preferably 20 m ² / g or less, 10 m ² / g or less, or 5 m ² / g or less. The specific surface area of the inorganic filler is calculated according to the BET method by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co.) and using the BET multipoint method. Obtained by:

  The content of the inorganic filler (D) with respect to the entire resin composition is preferably 60% by mass or more, from the viewpoint of further improving the effect of the present invention, when the nonvolatile component in the resin composition is 100% by mass. It is preferably at least 70% by mass, more preferably at least 75% by mass, particularly preferably at least 80% by mass. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less, from the viewpoint of the mechanical strength of the obtained cured product.

<(E) Other epoxy resins>
The resin composition according to the present invention optionally contains (E) another epoxy resin other than the (A) component and the (B) component.

  (E) Other epoxy resins include, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, tris Phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type Epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, Pyro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. Among them, bisphenol A type epoxy resin is preferable. The epoxy resin may be used alone or in a combination of two or more.

  When (E) other epoxy resin is contained, the resin composition comprises, as (E) other epoxy resin, an epoxy resin other than the component (A) and the component (B) having two or more epoxy groups in one molecule. It is preferable to include From the viewpoint of remarkably obtaining the desired effects of the present invention, the component (A) having two or more epoxy groups in one molecule and the component (B) having 100 or more non-volatile components of the epoxy resin (E). The proportion of the epoxy resin other than the components is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

  (E) Other epoxy resins include a liquid epoxy resin at a temperature of 20 ° C (hereinafter sometimes referred to as “liquid epoxy resin”) and a solid epoxy resin at a temperature of 20 ° C (hereinafter “solid epoxy resin”). There is.) The resin composition may contain only the liquid epoxy resin as the (E) other epoxy resin, or may contain only the solid epoxy resin.

  As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

  Examples of the liquid epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin, phenol novolak epoxy resin, and alicyclic epoxy resin having an ester skeleton. , A cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are more preferable.

  Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, and “HP4032SS” (naphthalene-type epoxy resin) manufactured by DIC; “EXA-850CRP” manufactured by DIC; “828US” manufactured by Mitsubishi Chemical Corporation; "JER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol) manufactured by Mitsubishi Chemical Corporation "Novolak type epoxy resin"; "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin). ; "Cell" manufactured by Daicel "Xide 2021P" (an alicyclic epoxy resin having an ester skeleton); "PB-3600" (an epoxy resin having a butadiene structure) manufactured by Daicel Corporation; "ZX1658" and "ZX1658GS" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 4-glycidylcyclohexane type epoxy resin) and the like. These may be used alone or in combination of two or more.

  As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

  Examples of the solid epoxy resin include a bixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type epoxy resin is more preferable.

  Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type four-functional epoxy resin) manufactured by DIC; "N-690" (cresol novolak type epoxy resin); DIC "N-695" (cresol novolak type epoxy resin); DIC "HP-7200" (dicyclopentadiene type epoxy resin); “HP-7200HH”, “HP-7200H”, “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” (manufactured by DIC Corporation) Naphthylene ether type epoxy resin); "EPPN-502H" (Trisphenol type epoxy resin) manufactured by Nippon Kayaku Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolak type epoxy resin); Nippon Kayaku Co., Ltd. "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); Nippon Steel & Sumitomo Metal Corporation "ESN475V" (naphthol type epoxy resin) manufactured by Chemical Company; "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation; "YX4000H", "YX4000", "YL6121" (biphenyl type) manufactured by Mitsubishi Chemical Corporation. "Epoxy resin"; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-" manufactured by Osaka Gas Chemical Company. 500 ”;“ YL ”manufactured by Mitsubishi Chemical Corporation 760 "(bisphenol AF type epoxy resin);" YL7800 "(fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation;" jER1010 "(solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation;" jER1031S "manufactured by Mitsubishi Chemical Corporation (Tetraphenylethane-type epoxy resin). These may be used alone or in combination of two or more.

  (E) When a liquid epoxy resin and a solid epoxy resin are used in combination as the other epoxy resins, their quantitative ratio (liquid epoxy resin: solid epoxy resin) is preferably 1: 1 to 1 in terms of mass ratio. : 20, more preferably 1: 1 to 1:10, particularly preferably 1: 1 to 1: 5. When the ratio between the liquid epoxy resin and the solid epoxy resin is within the above range, the desired effects of the present invention can be remarkably obtained.

  (E) The epoxy equivalent of the other epoxy resin is preferably 50 g / eq to 5000 g / eq, more preferably 50 g / eq to 3000 g / eq, still more preferably 80 g / eq to 2000 g / eq, and even more preferably 100 g / eq. eq to 1000 g / eq. Within this range, the crosslinked density of the cured product of the resin composition layer becomes sufficient, and an insulating layer with small surface roughness can be provided. Epoxy equivalent is the weight of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

  (E) The weight average molecular weight (Mw) of the other epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, and still more preferably from 400 to 1500, from the viewpoint of obtaining the desired effect of the present invention remarkably. . The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

  (E) The content of the other epoxy resin is not particularly limited, but is preferably from the viewpoint of obtaining the desired effect of the present invention remarkably when the resin component in the resin composition is 100% by mass. Is at most 20% by mass, more preferably at most 15% by mass, further preferably at most 10% by mass, particularly preferably at most 6% by mass. When the resin composition contains (E) another epoxy resin, the lower limit may be 1% by mass or more.

<(F) Other additives>
The resin composition according to the present invention may further contain other additives as optional components in addition to the components described above. Such additives include components known to those skilled in the art, for example, organic fillers; thermoplastic resins; resins such as polymerization initiators, flame retardants, thickeners, defoamers, leveling agents, and adhesion promoters. Additives; and the like. These additives may be used alone or in a combination of two or more. Those skilled in the art can appropriately set the respective contents.

<Preparation and physical properties of resin composition>
The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of adding a solvent or the like as necessary to the components to be mixed and dispersed using a rotary mixer or the like.

  ADVANTAGE OF THE INVENTION According to the resin composition which concerns on this invention, a hardened | cured material which can suppress a warp and can suppress a dielectric loss tangent low even after being put under high temperature and high humidity for a long time can be obtained.

  The amount of warpage of the cured product is preferably as small as possible, and as a value calculated by measuring based on JEITA EDX-7311-24 of the Japan Electronics and Information Technology Industries Association, preferably less than 3 mm, more preferably less than 2 mm, and more preferably 1 mm Less than is more preferred.

  The dielectric loss tangent (tan δ) of the cured product after HAST is preferably less than 0.0074, more preferably less than 0.0072, and even more preferably less than 0.0070. On the other hand, the lower limit value of the dielectric loss tangent is not particularly limited, but may be 0.0001 or more. The evaluation of the dielectric loss tangent can be measured according to the method described in Examples described later.

  The resin composition of the present invention can suppress warpage and can provide an insulating layer having a low dielectric loss tangent even after being placed under high temperature and high humidity for a long time. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating applications. Specifically, a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer (a resin for forming an insulating layer for forming a conductor layer) Composition). Further, in a printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of the printed wiring board (resin composition for forming an insulating layer of the printed wiring board). The resin composition of the present invention also requires a resin composition, such as an adhesive film, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a filling resin, and a component filling resin. It can be used in a wide range of applications.

<Semiconductor chip package>
The semiconductor chip package according to the first embodiment of the present invention includes a printed wiring board described later, a semiconductor chip mounted on the printed wiring board, and a sealing resin composition for sealing the semiconductor chip. And cured products. This semiconductor chip package can be manufactured by joining a semiconductor chip to a printed wiring board.

  The sealing of the semiconductor chip can be performed by a method similar to the step (C) in the second embodiment described later.

  As the bonding condition between the printed wiring board and the semiconductor chip, any condition can be adopted in which the terminal electrodes of the semiconductor chip and the circuit wiring of the printed wiring board can be electrically connected. For example, conditions used in flip chip mounting of a semiconductor chip can be adopted. Further, for example, the semiconductor chip and the printed wiring board may be joined via an insulating adhesive.

  As an example of the joining method, a method of crimping a semiconductor chip to a printed wiring board is given. As the crimping conditions, the crimping temperature is usually in a range of 120 ° C to 240 ° C (preferably in a range of 130 ° C to 200 ° C, more preferably in a range of 140 ° C to 180 ° C), and the crimping time is usually in a range of 1 second to 60 seconds. (Preferably 5 seconds to 30 seconds).

  Another example of the joining method includes a method of joining a semiconductor chip by reflowing it on a printed wiring board. Reflow conditions may be in the range of 120C to 300C.

  After joining the semiconductor chip to the printed wiring board, the semiconductor chip may be filled with a mold underfill material. The resin composition described above may be used as the mold underfill material, or an adhesive film described below may be used.

  A semiconductor chip package according to a second embodiment of the present invention includes a semiconductor chip and a cured product of the sealing resin composition for sealing the semiconductor chip. As the semiconductor chip package according to the second embodiment, for example, a Fan-out type WLP is used.

The manufacturing method of such a semiconductor chip package is as follows.
(A) a step of laminating a temporary fixing film on a substrate,
(B) temporarily fixing the semiconductor chip on the temporary fixing film;
(C) forming a sealing layer on the semiconductor chip;
(D) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;
(E) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off;
(F) a step of forming a rewiring layer as a conductor layer on the rewiring forming layer, and
(G) forming a solder resist layer on the rewiring layer;
including. Further, the method of manufacturing a semiconductor chip package described above,
(H) The method may include a step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages to singulate.

(Step (A))
Step (A) is a step of laminating a temporary fixing film on a substrate. The conditions for laminating the base material and the temporary fixing film may be the same as the conditions for laminating the interior substrate and the adhesive film in the method for manufacturing a printed wiring board.

  As the base material, for example, a silicon wafer; a glass wafer; a glass substrate; a metal substrate such as copper, titanium, stainless steel, or a cold rolled steel plate (SPCC); A substrate made of bismaleimide triazine resin such as BT resin; and the like.

  The temporary fixing film can be made of any material that can be peeled off from the semiconductor chip and can temporarily fix the semiconductor chip. Examples of commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

(Step (B))
Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. The temporary fixation of the semiconductor chip can be performed using, for example, a device such as a flip chip bonder or a die bonder. The layout and the number of semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, and the like. For example, the semiconductor chips may be arranged in a matrix of a plurality of rows and a plurality of columns and temporarily fixed.

(Step (C))
Step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer is formed from a cured product of the above-described sealing resin composition. The sealing layer is generally formed by a method including a step of forming a sealing resin composition layer on a semiconductor chip and a step of thermally curing the resin composition layer to form a sealing layer.

  The resin composition layer is preferably formed by a compression molding method, utilizing the excellent compression moldability of the sealing resin composition. In the compression molding method, usually, a semiconductor chip and a resin composition are arranged in a mold, and a pressure and, if necessary, heat are applied to the sealing resin composition in the mold to form a resin composition layer covering the semiconductor chip. Form.

  The specific operation of the compression molding method can be, for example, as follows. An upper die and a lower die are prepared as compression molding dies. Further, the sealing resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the sealing resin composition is attached to a lower mold together with the base material and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped, and heat and pressure are applied to the sealing resin composition to perform compression molding.

  The specific operation of the compression molding method may be, for example, as follows. An upper die and a lower die are prepared as compression molding dies. The sealing resin composition is placed on the lower mold. Further, the semiconductor chip is attached to the upper mold together with the base material and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped so that the sealing resin composition placed on the lower mold is in contact with the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

  Molding conditions vary depending on the composition of the sealing resin composition, and appropriate conditions can be adopted so that good sealing is achieved. For example, the temperature of the mold during molding is preferably a temperature at which the sealing resin composition can exhibit excellent compression moldability, preferably 80 ° C or higher, more preferably 100 ° C or higher, and particularly preferably 120 ° C or higher. , Preferably 200 ° C or lower, more preferably 170 ° C or lower, particularly preferably 150 ° C or lower. The pressure applied during molding is preferably at least 1 MPa, more preferably at least 3 MPa, particularly preferably at least 5 MPa, preferably at most 50 MPa, more preferably at most 30 MPa, particularly preferably at most 20 MPa. The cure time is preferably at least 1 minute, more preferably at least 2 minutes, particularly preferably at least 5 minutes, preferably at most 60 minutes, more preferably at most 30 minutes, particularly preferably at most 20 minutes. Usually, the mold is removed after the formation of the resin composition layer. The removal of the mold may be performed before or after the thermosetting of the resin composition layer.

  The compression molding method may be performed by discharging the sealing resin composition filled in the cartridge into a lower mold. The molding conditions after the formation of the resin composition layer are the same as those in the compression molding.

  The resin composition layer may be formed by laminating an adhesive film and a semiconductor chip. For example, the resin composition layer of the adhesive film and the semiconductor chip are heat-pressed to form a resin composition layer on the semiconductor chip. The lamination of the adhesive film and the semiconductor chip can be generally performed in the same manner as the lamination of the adhesive film and the interior substrate in the method of manufacturing a printed wiring board, using the semiconductor chip instead of the base material.

  After forming the resin composition layer on the semiconductor chip, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor chip. Thereby, the semiconductor chip is sealed with the cured product of the sealing resin composition. The thermosetting conditions of the resin composition layer may be the same as the thermosetting conditions of the resin composition layer in the method for manufacturing a printed wiring board. Further, before heat curing the resin composition layer, the resin composition layer may be subjected to a preliminary heating treatment of heating at a temperature lower than the curing temperature. The processing conditions of this preheating treatment may be the same as those of the preheating treatment in the method for manufacturing a printed wiring board.

(Step (D))
Step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor chip. As the peeling method, it is desirable to adopt an appropriate method according to the material of the temporary fixing film. Examples of the peeling method include a method of heating, foaming, or expanding the temporary fixing film to peel it off. Examples of the peeling method include a method of irradiating the temporary fixing film with ultraviolet rays through the base material to reduce the adhesive force of the temporary fixing film and peeling the temporary fixing film.

In the method in which the temporary fixing film is heated, foamed or expanded and peeled off, the heating condition is usually 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. Further, in the method for peeling by reducing the adhesive strength of the temporary fixing film by ultraviolet irradiation, irradiation amount of ultraviolet rays is ^{usually, 10mJ / cm 2 ~1000mJ / cm} 2.

(Step (E))
The step (E) is a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off.

  Any material having an insulating property can be used as the material of the rewiring formation layer. Among them, a photosensitive resin and a thermosetting resin are preferable from the viewpoint of ease of manufacturing a semiconductor chip package. Further, as the thermosetting resin, the sealing resin composition of the present invention may be used.

  After forming the rewiring formation layer, a via hole may be formed in the rewiring formation layer in order to connect the semiconductor chip and the rewiring layer between layers.

  In the method of forming a via hole when the material of the rewiring formation layer is a photosensitive resin, the surface of the rewiring formation layer is usually irradiated with an active energy ray through a mask pattern, and the irradiated portion of the rewiring formation layer is irradiated with light. Let it cure. Examples of the active energy ray include an ultraviolet ray, a visible ray, an electron beam, an X-ray, and the like, and an ultraviolet ray is particularly preferable. The irradiation amount and irradiation time of the ultraviolet ray can be appropriately set according to the photosensitive resin. Examples of the exposure method include, for example, a contact exposure method in which a mask pattern is brought into close contact with a rewiring formation layer and exposure, a non-contact exposure method in which a mask pattern is exposed using parallel rays without being brought into close contact with a rewiring formation layer, and the like. Is mentioned.

  After the rewiring formation layer is photo-cured, the rewiring formation layer is developed, and the unexposed portions are removed to form via holes. The development may be either wet development or dry development. Examples of the development method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and a paddle method is preferable from the viewpoint of resolution.

  When the material of the rewiring formation layer is a thermosetting resin, examples of a method of forming a via hole include laser irradiation, etching, and mechanical drilling. Among them, laser irradiation is preferable. Laser irradiation can be performed using an appropriate laser beam machine using a light source such as a carbon dioxide laser, a UV-YAG laser, and an excimer laser.

  The shape of the via hole is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, further preferably 20 μm or less, preferably 3 μm or more, preferably 10 μm or more, and more preferably 15 μm or more. Here, the top diameter of the via hole refers to the diameter of the opening of the via hole on the surface of the rewiring formation layer.

(Step (F))
Step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring forming layer. The method for forming the rewiring layer on the rewiring forming layer can be the same as the method for forming the conductor layer on the insulating layer in the method for manufacturing a printed wiring board. Further, the steps (E) and (F) may be repeatedly performed to alternately build up the rewiring layers and the rewiring forming layers (build-up).

(Step (G))
Step (G) is a step of forming a solder resist layer on the rewiring layer. Any material having an insulating property can be used as a material for the solder resist layer. Among them, a photosensitive resin and a thermosetting resin are preferable from the viewpoint of ease of manufacturing a semiconductor chip package. Moreover, you may use the resin composition for sealing of this invention as a thermosetting resin.

  In the step (G), bumping processing for forming a bump may be performed as necessary. The bumping process can be performed by a method such as solder ball or solder plating. The formation of via holes in the bumping process can be performed in the same manner as in the step (E).

  The method for manufacturing a semiconductor chip package may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages to singulate them. The method of dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited.

  The semiconductor chip package according to the third embodiment of the present invention is, for example, a semiconductor chip package according to the second embodiment, in which a rewiring formation layer or a solder resist layer is formed from a cured product of the resin composition of the present invention. It is.

<Sheet laminated material>
The resin composition of the present invention can be used after being applied in a liquid state, but can also be used in the form of a sheet-like laminated material containing the resin composition.

  As the sheet-like laminated material, the following adhesive films and prepregs are preferable.

  In one embodiment, the adhesive film includes a support and a resin composition layer (adhesive layer) bonded to the support, wherein the resin composition layer (adhesive layer) is a resin composition of the present invention. Formed from

  The thickness of the resin composition layer is preferably 50 μm or less, from the viewpoint that the thickness of the printed wiring board can be reduced, and a cured product having excellent insulating properties can be provided even when the cured product of the resin composition is a thin film. Preferably it is 40 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 5 μm or more, 10 μm or more, or the like.

  Examples of the support include a film made of a plastic material, a metal foil, and release paper, and a film made of a plastic material and a metal foil are preferable.

  When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) or polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). .), Acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), and polyethers. Ketone, polyimide and the like can be mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. May be used.

  The support may have been subjected to a mat treatment, a corona treatment, or an antistatic treatment on the surface to be joined to the resin composition layer.

  Further, as the support, a support with a release layer having a release layer on the surface to be joined to the resin composition layer may be used. Examples of the release agent used in the release layer of the support having a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . The support with a release layer may be a commercially available product, for example, "SK-1" manufactured by Lintec, which is a PET film having a release layer containing an alkyd resin-based release agent as a main component. AL-5 "," AL-7 "," Lumirror T60 "manufactured by Toray Industries," Purex "manufactured by Teijin Limited," Unipeal "manufactured by Unitika, and the like.

  The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the support with a release layer is preferably within the above range.

  In one embodiment, the adhesive film may further include any optional layers. Examples of such an optional layer include a protective film according to the support provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Can be Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the attachment and scratches of dust and the like to the surface of the resin composition layer.

  The adhesive film is prepared, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, applying the resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer. It can be manufactured by the following.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol Carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

  Drying may be performed by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of an organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. An object layer can be formed.

  The adhesive film can be wound into a roll and stored. When the adhesive film has a protective film, it can be used by peeling off the protective film.

  In one embodiment, the prepreg is formed by impregnating the resin composition of the present invention into a sheet-like fiber base material.

  The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as a prepreg base material such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber substrate is not particularly limited. Usually, it is 10 μm or more.

  The prepreg can be manufactured by a known method such as a hot melt method and a solvent method.

  The thickness of the prepreg can be in the same range as the resin composition layer in the above-mentioned adhesive film.

  In the present invention using a resin composition containing a combination of the component (A), the component (B), the component (C), and the component (D) at a specific content, the warpage can be suppressed, and the composition can be used under high temperature and high humidity. Since a cured product having a low dielectric loss tangent can be obtained even after being placed for a long time, a sheet-like laminated material which is extremely useful in manufacturing a printed wiring board can be realized.

  The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (printing). (For an interlayer insulating layer of a wiring board).

<Printed wiring board>
The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

The printed wiring board can be manufactured by a method including the following steps (I) and (II) using the above-mentioned adhesive film, for example.
(I) Step of laminating an adhesive film on the inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate (II) Curing (for example, heat curing) the resin composition layer to form an insulating layer Process

  The “inner layer substrate” used in the step (I) is a member to be a substrate of a printed wiring board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate And the like. Further, the substrate may have a conductor layer on one or both surfaces thereof, and the conductor layer may be patterned. An inner substrate having a conductor layer (circuit) formed on one or both surfaces of the substrate may be referred to as an “inner circuit substrate”. In the manufacture of a printed wiring board, an intermediate product on which an insulating layer and / or a conductor layer is to be formed is also included in the “inner substrate” of the present invention. When the printed wiring board is a component built-in circuit board, an inner layer board in which components are built may be used.

  The lamination of the inner layer substrate and the adhesive film can be performed, for example, by heat-pressing the adhesive film to the inner layer substrate from the support side. Examples of a member (hereinafter, also referred to as a “thermocompression member”) for thermocompression bonding the adhesive film to the inner layer substrate include a heated metal plate (SUS mirror plate or the like) or a metal roll (SUS roll). It is preferable that the thermocompression bonding member is not pressed directly on the adhesive film, but is pressed via an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the surface irregularities of the inner substrate.

  The lamination of the inner substrate and the adhesive film may be performed by a vacuum lamination method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in a range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098MPa to 1.77MPa, more preferably 0mm. .29 MPa to 1.47 MPa, and the heat-compression bonding time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure condition of a pressure of 26.7 hPa or less.

  Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials Co., Ltd., and a batch vacuum pressurized laminator.

  After lamination, the laminated adhesive film may be subjected to a smoothing process under normal pressure (under atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same as the conditions for the thermocompression bonding of the lamination. The smoothing treatment can be performed with a commercially available laminator. Note that the lamination and the smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

  The support may be removed between step (I) and step (II), or may be removed after step (II).

  In the step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer. The curing conditions of the resin composition layer are not particularly limited, and conditions usually employed for forming an insulating layer of a printed wiring board may be used.

  For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition and the like, but the curing temperature is preferably 120 ° C to 240 ° C, more preferably 150 ° C to 220 ° C, and still more preferably 170 ° C to 210 ° C. ° C. The curing time can be preferably from 5 minutes to 120 minutes, more preferably from 10 minutes to 100 minutes, even more preferably from 15 minutes to 100 minutes.

  Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is heated at a temperature of 50 ° C. or more and less than 120 ° C., preferably 60 ° C. or more and less than 115 ° C., more preferably 70 ° C. or more and less than 110 ° C. Preheating may be performed for at least one minute, preferably for 5 to 150 minutes, more preferably for 15 to 120 minutes, and still more preferably for 15 to 100 minutes.

  In manufacturing the printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) may be performed according to various methods used for manufacturing a printed wiring board and known to those skilled in the art. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or It may be performed between IV) and step (V). If necessary, the formation of the insulating layer and the conductor layer in the steps (II) to (V) may be repeated to form a multilayer wiring board.

  In another embodiment, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as the case where an adhesive film is used.

  The step (III) is a step of forming a hole in the insulating layer, whereby a hole such as a via hole or a through hole can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole may be appropriately determined according to the design of the printed wiring board.

  Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear is also removed. The procedure and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions usually used when forming an insulating layer of a printed wiring board can be adopted. For example, a swelling process using a swelling solution, a roughening process using an oxidizing agent, and a neutralizing process using a neutralizing solution can be performed in this order to roughen the insulating layer.

  The swelling solution used for the roughening treatment is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, and are preferably an alkali solution.As the alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C to 80 ° C for 5 minutes to 15 minutes.

  The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C to 100 ° C for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganate solution is preferably from 5% by mass to 10% by mass. Commercially available oxidizing agents include, for example, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan.

  The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include “Reduction Solution Securiganto P” manufactured by Atotech Japan.

  The treatment with the neutralizing solution can be performed by immersing the roughened surface with the oxidizing agent in the neutralizing solution at 30 ° C. to 80 ° C. for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method in which the object roughened by the oxidizing agent is immersed in a neutralizing solution at 40 ° C to 70 ° C for 5 to 20 minutes is preferable.

  In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. The lower limit is not particularly limited, but may be preferably 0.5 nm or more, more preferably 1 nm or more. The root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, but may be preferably 0.5 nm or more, more preferably 1 nm or more. The arithmetic average roughness (Ra) and the root-mean-square roughness (Rq) of the insulating layer surface can be measured using a non-contact type surface roughness meter.

  Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductive layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Including metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper Nickel alloy and copper-titanium alloy). Among them, from the viewpoints of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper A nickel alloy or an alloy layer of copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferable. Metal layers are more preferred.

  The conductor layer may have a single-layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are stacked. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

  The thickness of the conductive layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

  In one embodiment, the conductor layer may be formed by plating. For example, a semi-additive method, plating on the surface of the insulating layer by a conventionally known technique such as a full-additive method can form a conductor layer having a desired wiring pattern. It is preferably formed by a method. Hereinafter, an example in which a conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like, so that a conductor layer having a desired wiring pattern can be formed.

  In another embodiment, the conductor layer may be formed using a metal foil. When a conductor layer is formed using a metal foil, step (V) is preferably performed between step (I) and step (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. The lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The conditions for lamination may be the same as those described for the step (I). Next, the step (II) is performed to form an insulating layer. After that, a conductor layer having a desired wiring pattern can be formed by using a metal foil on the insulating layer and using a conventional known technique such as a subtractive method or a modified semi-additive method.

  The metal foil can be manufactured by a known method such as an electrolytic method and a rolling method. Commercially available metal foils include, for example, HLP foil, JXUT-III foil, 3EC-III foil, TP-III foil, etc., manufactured by JX Nippon Mining & Metals Co., Ltd.

  When manufacturing a printed wiring board using the resin composition of the present invention containing a specific content of the combination of the component (A), the component (B), the component (C), and the component (D), Regardless of whether it is formed by plating or using a metal foil, the dielectric loss tangent can be kept low even after being placed under high temperature and high humidity for a long time.

<Semiconductor device>
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

  Examples of the semiconductor device include various semiconductor devices used for electric appliances (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction point” is a “point where an electric signal is transmitted on the printed wiring board”, and the point may be a surface or an embedded point. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, a wire bonding mounting method, a flip chip mounting method, a bumpless build-up layer, and the like. (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the “mounting method using the bump-less build-up layer (BBUL)” refers to a “mounting method for directly embedding a semiconductor chip in a recess of a printed wiring board and connecting the semiconductor chip to wiring on the printed wiring board”. It is.

  Hereinafter, the present invention will be described specifically with reference to examples. However, the present invention is not limited to the embodiments described below. In the following description, “parts” and “%” representing amounts mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

  First, a measurement / evaluation method in the physical property evaluation in the present specification will be described.

<Evaluation of warpage>
The resin compositions produced in the following Examples and Comparative Examples were compression-molded on a 12-inch silicon wafer using a compression molding apparatus (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes). And a resin composition layer having a thickness of 300 μm. Thereafter, heating was performed at 180 ° C. for 90 minutes to thermally cure the resin composition layer. As a result, a sample substrate including the silicon wafer and the cured product layer of the resin composition was obtained. The amount of warpage of the sample substrate at 25 ° C. was measured using a shadow moire measuring device (“ThermoireAXP” manufactured by Akorometrix). The measurement was performed according to JEITA EDX-7311-24 of the Japan Electronics and Information Technology Industries Association standard. Specifically, a virtual plane calculated by the least square method of all data on the substrate surface in the measurement area was used as a reference plane, and the difference between the minimum value and the maximum value in the vertical direction from the reference plane was obtained as the amount of warpage. A degree of warpage of less than 2 mm was judged as “○”, 2 mm or more and less than 3 mm as “Δ”, and 3 mm or more as “X”.

<Dielectric loss tangent after high temperature and high humidity environment test (HAST)>
On a SUS plate whose surface has been subjected to a mold release treatment, the resin compositions produced in the following Examples and Comparative Examples are compression-molded (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes). To form a resin composition layer having a thickness of 300 μm. The SUS plate was peeled off, and the resin composition layer was thermally cured by heating at 180 ° C. for 90 minutes to obtain a cured resin composition. Thereafter, the cured product was subjected to a high temperature and high humidity environment test (HAST) under the conditions of 130 ° C. and 85% RH for 100 hours. The cured product after the HAST was cut into test pieces having a width of 2 mm and a length of 80 mm, and a cavity resonator perturbation method dielectric constant measuring device CP521 manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technology Co., Ltd. were used. The dielectric tangent (tan δ) was measured at a measurement frequency of 5.8 GHz by the cavity resonance method. The measurement was performed on two test pieces, and the average value was calculated. When the average value of the dielectric loss tangent was less than 0.0070, it was evaluated as “◎”, when it was 0.0070 or more and less than 0.0074, it was evaluated as “○”, and when it was 0.0074 or more, it was evaluated as “x”.

<Example 1>
3 parts of glycidylamine type epoxy resin (“EP3980S” manufactured by ADEKA, epoxy equivalent 115 g / eq.), 6 parts of glycidylamine type epoxy resin (“630LSD” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 95 g / eq.), Polyvalent glycidyl 4 parts of compound ("BATG" manufactured by Showa Denko KK, epoxy equivalent: 119 g / eq.), 4 parts of bisphenol A type epoxy resin ("EXA-850CRP" manufactured by DIC, epoxy equivalent: 170-175 g / eq.), Phenol-based curing 1 part of an agent (“MEH-8000H” manufactured by Meiwa Kasei) and spherical silica (average particle size 4.8 μm, maximum cut diameter 20 μm) treated with KBM403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) a specific surface area of 3.9m ² / g) 83 parts of 2-ethyl-4-methylimidazole Shikoku Kasei Co., Ltd. "2E4MZ") 0.4 parts, uniformly dispersed using a mixer to obtain a resin composition.

<Example 2>
The compounding amount of the glycidylamine type epoxy resin (“630” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 95 g / eq.) Was changed from 6 parts to 2 parts, and the bisphenol A type epoxy resin (“EXA-850CRP” manufactured by DIC), epoxy A resin composition was obtained in the same manner as in Example 1, except that the amount of the equivalent (170 to 175 g / eq.) Was changed from 4 parts to 8 parts.

<Example 3>
The compounding amount of the glycidylamine type epoxy resin (“630” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 95 g / eq.) Was changed from 6 parts to 10 parts, and the bisphenol A type epoxy resin (“EXA-850CRP” manufactured by DIC), epoxy Except not using an equivalent of 170 to 175 g / eq.), A resin composition was obtained in the same manner as in Example 1.

<Example 4>
Except that 1 part of a phenolic curing agent (“MEH-8000H” manufactured by Meiwa Kasei) was changed to 1 part of an amine-based curing agent (“Kayabond C-200S” manufactured by Nippon Kayaku Co., Ltd.), the same as in Example 1 was performed. A resin composition was obtained.

<Example 5>
2 parts of glycidylamine type epoxy resin (“EP3980S” manufactured by ADEKA, epoxy equivalent 115 g / eq.), 3 parts of glycidylamine type epoxy resin (“630” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 95 g / eq.), Polyvalent glycidyl 1 part of compound ("BATG" manufactured by Showa Denko KK, epoxy equivalent 119 g / eq.), 6 parts bisphenol A type epoxy resin (EXA-850CRP manufactured by DIC, epoxy equivalent 170-175 g / eq.), Acid anhydride Spherical silica (average particle size) treated with 6 parts of a curing agent (“HNA-100” manufactured by Nippon Rika Co., Ltd., acid anhydride equivalent 179) and KBM403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) diameter 4.8 .mu.m, the maximum cutting diameter 20 [mu] m, a specific surface area of 3.9m ² / g) 83 parts of 2-ethyl-4-Mechirui The indazole (Shikoku Kasei Co., Ltd., "2E4MZ") 0.1 parts, uniformly dispersed using a mixer to obtain a resin composition.

<Comparative Example 1>
The compounding amount of the polyvalent glycidyl compound ("BATG" manufactured by Showa Denko KK, epoxy equivalent 119 g / eq.) Was changed from 4 parts to 0.2 part, and the phenolic curing agent ("MEH-8000H" manufactured by Meiwa Kasei) was changed. A resin composition was obtained in the same manner as in Example 1, except that the amount was changed from 1 part to 4 parts.

<Comparative Example 2>
6 parts of glycidylamine type epoxy resin (“630” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g / eq.), 7 parts of polyvalent glycidyl compound (“BATG” manufactured by Showa Denko, epoxy equivalent: 119 g / eq.), Bisphenol A type 1 part of epoxy resin (“EXA-850CRP” manufactured by DIC, epoxy equivalent: 170 to 175 g / eq.), 4 parts of phenolic curing agent (“MEH-8000H” manufactured by Meiwa Kasei), KBM403 (3-glycidoxypropyltri) 83 parts of spherical silica (average particle size 4.8 μm, maximum cut diameter 20 μm, specific surface area 3.9 m ² / g) treated with methoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., 2-ethyl-4-methylimidazole (Shikoku) 0.4 parts of “2E4MZ” manufactured by Kasei Co., Ltd. was uniformly dispersed using a mixer to obtain a resin composition.

  Table 1 shows the evaluation results of the examples and the comparative examples.

  According to the above results, by including the component (A), the component (B), the component (C), and the component (D) in a specific content in the resin composition, warpage can be suppressed, and the resin composition can be obtained under high temperature and high humidity. It can be seen that a cured product having a low dielectric loss tangent can be obtained even after being placed for a long time.

Claims (10)

(A) glycidylamine type epoxy resin,
(B) a polyvalent glycidyl compound having an aromatic ring in which a glycidyl group and a glycidyloxy group are each directly bonded,
(C) a curing agent, and (D) a resin composition containing an inorganic filler,
When the nonvolatile component in the resin composition is 100% by mass, the content of the component (A) is 3% by mass to 15% by mass,
When the nonvolatile component in the resin composition is 100% by mass, the content of the component (B) is from 0.2% by mass to 6.5% by mass.   The resin composition according to claim 1, wherein the content of the component (A) is 5% by mass to 10% by mass when the nonvolatile component in the resin composition is 100% by mass.   The resin composition according to claim 1, wherein the component (C) is selected from the group consisting of a phenol-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, and an imidazole-based curing agent.   The resin composition according to any one of claims 1 to 3, wherein the content of the component (D) is 80% by mass or more when the nonvolatile component in the resin composition is 100% by mass.   The resin composition according to any one of claims 1 to 4, which is used for forming an insulating layer for forming a conductor layer.   The resin composition according to any one of claims 1 to 4, which is for sealing a semiconductor chip.   A sheet-like laminated material comprising the resin composition according to claim 1.   A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to claim 1.   A semiconductor chip package comprising a cured product of the resin composition according to claim 1.   A semiconductor device comprising a cured product of the resin composition according to claim 1.