JP7163654B2 - Resin composition, sheet-like laminate material, printed wiring board, semiconductor chip package, and semiconductor device - Google Patents

Description

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

In recent years, there has been an increase in demand for small, highly functional electronic devices such as smart phones and tablet-type devices, and along with this, insulating materials used in these small electronic devices are also required to have higher functionality. As such an insulating material, for example, a material formed by curing a resin composition is known (see Patent Document 1, for example).

JP 2015-127397 A

In recent years, there has been a demand for a smaller semiconductor chip package, and accordingly, it is required to reduce the thickness of the insulating layer used in the semiconductor chip package and the silicon chip itself. Therefore, it is desired to develop an insulating layer that can suppress warping even if the thickness is thin. 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, conventional resin compositions still have room for improvement in the evaluation of warpage and dielectric loss tangent of the cured product.

The present invention provides a resin composition capable of suppressing warping and capable of 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; A semiconductor chip package containing the cured product; and a semiconductor device containing the cured product.

As a result of intensive studies on the above problems, the present inventors have found that the above-mentioned We 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 to which a glycidyl group and a glycidyloxy group are directly bonded, (C) a curing agent, and (D) an inorganic filler Then, the resin composition, when the non-volatile 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 non-volatile component in the resin composition A resin composition in which the content of the component (B) is 0.2% by mass to 6.5% by mass when the is 100% by mass.
[2] The resin composition according to [1], wherein the content of component (A) is 5% by mass to 10% by mass when the non-volatile component in the resin composition is 100% by mass.
[3] The resin composition according to [1] or [2], wherein 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. thing.
[4] The resin according to any one of [1] to [3], wherein the content of component (D) is 80% by mass or more when the non-volatile 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 used for encapsulating semiconductor chips.
[7] A sheet-like laminate material containing the resin composition according to any one of [1] to [4].
[8] A printed wiring board comprising an insulating layer comprising 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 warping and capable of obtaining a cured product with 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 possible to provide a printed wiring board comprising an insulating layer made of the cured product; a semiconductor chip package containing the cured product; and a semiconductor device containing the cured product.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

<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 to which a glycidyl group and a glycidyloxy group are directly bonded, (C) a curing agent, and (D) When the inorganic filler is contained and the non-volatile component in the resin composition is 100% by mass, the content of component (A) is 3% by mass to 15% by mass, and the content of component (B) is 0.2 mass % to 6.5 mass %.

By using such a resin composition, it is possible to obtain the desired effect of the present invention that warping 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 components (A), (B), (C) and (D). Optional components include, for example, (E) other epoxy resins, and (F) other additives. Each component contained in the resin composition will be described in detail below.

<(A) Glycidylamine type epoxy resin>
The resin composition according to the present invention contains (A) a glycidylamine type epoxy resin. (A) Glycidylamine-type epoxy resin refers to an epoxy resin having at least one glycidylamino group and/or diglycidylamino group. A glycidylamino group contains one epoxy group, and a diglycidylamino group contains 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 2 or 3 epoxy groups in the molecule. Here, the epoxy group is not limited to those derived from a glycidylamino group and a diglycidylamino group, but may also include those derived from a glycidyloxy group. When the non-volatile component of the glycidylamine type epoxy resin is 100% by mass, the ratio of the difunctional or higher glycidylamine type epoxy resin is preferably 50% by mass or more, more preferably 60% by mass, from the viewpoint of increasing the heat resistance of the cured product. It is at least 70% by mass, more preferably at least 70% by mass.

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. As used herein, the term "aromatic ring" refers to an aromatic carbocyclic ring such as a benzene ring or naphthalene ring, or an aromatic heterocyclic ring such as a pyridine ring, pyrrole ring, furan ring or thiophene ring. When the molecule has two or more aromatic rings, the aromatic rings may be directly bonded or bonded via an oxygen atom, an alkylene group, a combination thereof, or the like.

As used herein, an alkylene group refers to a linear or branched divalent saturated aliphatic hydrocarbon group. An alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 1 to 5 carbon atoms is more preferred. Examples thereof include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, 1,1-dimethylethylene group, etc., and the bonding positions thereof are not particularly limited.

In component (A), the glycidylamino group and diglycidylamino group can be directly bonded to the aromatic ring. The aromatic ring may have other substituents in addition to the glycidylamino group and diglycidylamino group. Here, other substituents include, for example, a monovalent epoxy-containing group and a monovalent hydrocarbon group. A glycidyloxy group etc. are mentioned as a monovalent|monohydric epoxy containing group. Examples of monovalent hydrocarbon groups include alkyl groups and aryl groups.

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

As used herein, an aryl group refers to a monovalent aromatic hydrocarbon group. An aryl group having 6 to 14 carbon atoms is preferred, and an aryl group having 6 to 10 carbon atoms is more preferred. Examples include phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, 2-anthryl and the like.

(A) Component may be used individually by 1 type, and may be used in combination of 2 or more type.

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 formula (A-1), each 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, still more preferably 0 or 1, and particularly preferably 1. In formula (A-1), m represents an integer of 1-3. Among them, m is preferably 1 or 2, more preferably 1.

In formula (A-1), each R ¹¹ independently represents a monovalent epoxy-containing group such as a glycidyloxy group, or a monovalent hydrocarbon group such as an alkyl group or an aryl group. When R ¹¹ is a glycidyloxy group, R ¹¹ is preferably bonded at the para position relative to the bonding site between the nitrogen atom and the benzene ring. Moreover, when R ¹¹ is an alkyl group, it is preferably bonded at the ortho position with respect to 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 divalent hydrocarbon groups include an alkylene group and an arylene group. When m is 1, from the viewpoint of obtaining the desired effects of the present invention, R ¹² is preferably an alkyl group, more preferably a methyl group. Further, when m is 2, from the viewpoint of obtaining the desired effect of the present invention, R ¹² is preferably an alkylene group, more preferably a methylene group.

As used herein, an arylene group refers to a divalent aromatic hydrocarbon group. An arylene group having 6 to 14 carbon atoms is preferred, and an arylene group having 6 to 10 carbon atoms is more preferred. Examples include a phenylene group, a naphthylene group, a biphenylene group, and the like, and the bonding positions thereof are not particularly limited.

Specific examples of the component (A) include "630" and "630LSD" manufactured by Mitsubishi Chemical Corporation (as shown in formula (A-2) below), and "EP3980S" manufactured by ADEKA Corporation (of formula (A-3) below). Street), “EP3950S”, “EP3950L”, “ELM-100”, “ELM-100H”, “ELM-434”, “ELM-434L” manufactured by Sumitomo Chemical Co., Ltd., and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(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 crosslink density of the cured product of the resin composition is sufficient, and an insulating layer with a small surface roughness can be obtained.

(A) The weight average molecular weight (Mw) of the glycidylamine type epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500.

Assuming that the non-volatile component in the resin composition is 100% by mass, the content of component (A) in the resin composition is 3% by mass to 15% by mass. The content of component (A) is preferably 4% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more, from the viewpoint of suppressing warping of the cured product. The upper limit is preferably 12% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less, from the viewpoint of keeping the dielectric loss tangent of the cured product low after a high temperature and high humidity environment test (HAST).

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

(B) component may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

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

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

Specific examples of the component (B) include "BATG" manufactured by Showa Denko K.K. (according to formula (B-2) below).

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

(B) The polyvalent glycidyl compound preferably has a molecular weight of 100 to 5,000, more preferably 150 to 3,000, and still more preferably 200 to 1,500.

Assuming that the non-volatile component in the resin composition is 100% by mass, the content of component (B) in the resin composition is 0.2% by mass to 6.5% by mass. The content of 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 warping 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 keeping the dielectric loss tangent of the cured product low 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 the epoxy resin. Curing agents, cyanate ester curing agents, carbodiimide curing agents, phosphorus curing agents, amine curing agents, imidazole curing agents, guanidine curing agents, metal curing agents and the like can be used. Among them, from the viewpoint of obtaining the desired effect of the present invention, a curing agent selected from the group consisting of a phenolic curing agent, an acid anhydride curing agent, an amine curing agent, and an imidazole curing agent is preferred. preferable. (C) Curing agents may be used singly or in combination of two or more.

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

Acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-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- Examples thereof include dicarboxylic anhydrides (commercially available as "HNA-100" manufactured by Shin Nippon Rika Co., Ltd.), 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 contains an ester group with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more is preferably used. The active ester 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 curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolak are preferred. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentalene-phenylene.

Commercially available active ester curing agents include, as active ester compounds containing 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); active ester compounds containing naphthalene structures: "EXB9416-70BK" and "EXB -8150-65T" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated phenol novolak; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated phenol novolac "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that 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 benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; Examples include "Fa".

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4, 4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5- Difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, Polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. or a prepolymer that is entirely triazined to form a trimer), and the like.

Specific examples of carbodiimide curing agents include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd., and the like.

Examples of phosphorus-based curing agents include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like.

Examples of amine curing agents include triethylamine, tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5, 4,0)-undecene and the like, aliphatic amine curing agents such as 4-dimethylaminopyridine, 1,8-diazabicyclo(5,4,0)-undecene; benzidine, o-tolidine, 4,4' -diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane ("Kayabond C-100" manufactured by Nippon Kayaku as a commercial product), 4,4'-diamino-3,3'-diethyldiphenylmethane ("Kayahard AA" manufactured by Nippon Kayaku as a commercial product), 4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane (as a commercial product "Kayabond" manufactured by Nippon Kayaku) C-200S”), 4,4′-diamino-3,3′,5,5′-tetraethyldiphenylmethane (“Kayabond C-300S” manufactured by Nippon Kayaku as a commercial product), 4,4′-diamino- 3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 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-aminophenoxy)neopentane, 4,4′-[1,3-phenylenebis (1-Methyl-ethylidene)]bisaniline (commercially available as "bisaniline M" manufactured by Mitsui Chemicals), 4,4'-[1,4-phenylenebis(1-methyl-ethylidene)]bisaniline (commercially available "Bisaniline P" manufactured by Mitsui Chemicals), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (as a commercial product, "BAPP" manufactured by Wakayama Seika), 2,2-bis[4- (4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-bis(4-aminophenoxy)biphenyl and other aromatic amine curing agents.

Examples of imidazole curing agents include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2 -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 -phenylimidazolium 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 isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl -4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, Examples include imidazole compounds such as 2-phenylimidazoline and adducts of imidazole compounds and epoxy resins.

As the imidazole-based curing agent, a commercially available product may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Guanidine curing agents include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetra 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- allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like.

Metal-based curing agents include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

When a curing agent is included, the ratio of the epoxy resin to the curing agent is [total number of epoxy groups in the epoxy resin]:[total number of reactive groups in the curing agent], which is 1:0.2 to 1:1:0.2. A range of 2 is preferred, 1:0.3 to 1:1.5 is more preferred, and 1:0.4 to 1:1.2 is even more preferred. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and varies depending on the type of curing agent. The total number of epoxy groups in the epoxy resin is the sum of the values obtained by dividing the mass of the non-volatile components of each epoxy resin by the epoxy equivalent, and the total number of reactive groups in the curing agent is It is a value obtained by dividing the non-volatile component mass of each curing agent by the reactive group equivalent and totaling all the curing agents. By setting the ratio of the epoxy resin to the curing agent within this range, the heat resistance of the resulting cured product is further improved.

When the non-volatile component in the resin composition is 100% by mass, the content of component (C) in the resin composition is preferably 0.1% by mass or more, from the viewpoint of obtaining the desired effects of the present invention. It is preferably 0.5% by mass or more, more preferably 1% by mass or more. From the viewpoint of obtaining the desired effects of the present invention, the upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less.

<(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, but examples include 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 tungstate phosphate. Silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. (D) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

(D) Commercially available inorganic fillers include, for example, “UFP-30” manufactured by Denka Kagaku Kogyo; “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; 5N”; Admatechs “SC2500SQ”, “SO-C4”, “SO-C2”, “SO-C1”;

(D) The average particle size of the inorganic filler is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention, it is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and It is more preferably 6 µm or less, particularly preferably 5 µm or less. From the viewpoint of obtaining the desired effect of the present invention, 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, still more preferably 2 µm or more, still more preferably 3 µm or more, and particularly preferably 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 is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. A measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle diameter was calculated as the median diameter. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

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

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

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and further preferably 0.5 mg/m ² or less. 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 (eg, 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 liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. 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, and particularly preferably 3 m ² /g or more, from the viewpoint of further improving the effects of the present invention. Although there is no particular upper limit, it 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 determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area 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, more It is preferably 70% by mass or more, more preferably 75% by mass or more, and particularly preferably 80% by mass or more. 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 resulting cured product.

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

(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 novolac type epoxy resin, phenol novolac 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 novolac type Epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, and the like. Among them, bisphenol A type epoxy resin is preferable. Epoxy resins may be used singly or in combination of two or more.

(E) When other epoxy resins are included, the resin composition has two or more epoxy groups in one molecule as (E) other epoxy resins, other than component (A) and component (B). is preferably included. From the viewpoint of significantly obtaining the desired effects of the present invention, (E) component (A) and (B) having two or more epoxy groups per molecule with respect to 100% by mass of other epoxy resin non-volatile components The ratio 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 epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resins”) and epoxy resins that are solid at a temperature of 20°C (hereinafter referred to as “solid epoxy resins”). There is a thing.) The resin composition may contain only a liquid epoxy resin as (E) other epoxy resin, or may contain only a solid epoxy resin.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, phenol novolak type epoxy resin, and alicyclic epoxy resin having an ester skeleton. , cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure are preferable, and bisphenol A-type epoxy resins and bisphenol F-type epoxy resins are more preferable.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "EXA-850CRP" manufactured by DIC Corporation; "828US" manufactured by Mitsubishi Chemical Corporation; "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical; "jER152" manufactured by Mitsubishi Chemical (phenol 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) Daicel "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton); Daicel "PB-3600" (epoxy resin having a butadiene structure); Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1658", " ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin). These may be used individually by 1 type, and may be used in combination of 2 or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin, and more preferably naphthalene type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; DIC's "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( Naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; YX8800" (anthracene type epoxy resin); Osaka Gas Chemicals Co., Ltd. "PG-100", "CG-500"; Mitsubishi Chemical Co., Ltd. "YL7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical Co., Ltd. "YL7800 (fluorene type epoxy resin); Mitsubishi Chemical Corp.'s "jER1010" (solid bisphenol A type epoxy resin); Mitsubishi Chemical Corp.'s "jER1031S" (tetraphenylethane type epoxy resin). These may be used individually by 1 type, and may be used in combination of 2 or more types.

(E) When a combination of a liquid epoxy resin and a solid epoxy resin is used as the other epoxy resin, the ratio by mass (liquid epoxy resin: solid epoxy resin) is preferably 1:1 to 1. :20, more preferably 1:1 to 1:10, particularly preferably 1:1 to 1:5. The desired effect of the present invention can be remarkably obtained by setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range.

(E) The epoxy equivalent of other epoxy resins 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, still more preferably 100 g/eq. eq to 1000 g/eq. Within this range, the crosslink density of the cured product of the resin composition layer is sufficient, and an insulating layer with a small surface roughness can be obtained. Epoxy equivalent weight 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 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500, from the viewpoint of significantly obtaining the desired effects of the present invention. . The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of (E) other epoxy resin is not particularly limited, but is preferable from the viewpoint of significantly obtaining the desired effect of the present invention when the resin component in the resin composition is 100% by mass. is 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 6% by mass or less. When the resin composition contains (E) other epoxy resins, 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. Examples of such additives include components known to those skilled in the art, such as organic fillers; thermoplastic resins; additives; and the like. These additives may be used singly or in combination of two or more. Each content can be appropriately set by those skilled in the art.

<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 to the compounding ingredients, if necessary, and mixing and dispersing them using a rotating mixer or the like.

According to the resin composition of the present invention, it is possible to obtain a cured product that can suppress warpage and keep the dielectric loss tangent low even after being placed under high temperature and high humidity for a long time.

The amount of warpage of the cured product is preferably as small as possible, and the numerical value calculated by measuring based on the Japan Electronics and Information Technology Industries Association standard JEITA EDX-7311-24 is preferably less than 3 mm, more preferably less than 2 mm, and 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, still more preferably less than 0.0070. On the other hand, the lower limit of the dielectric loss tangent is not particularly limited, but may be 0.0001 or more. The dielectric loss tangent can be evaluated according to the method described in Examples below.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can suppress warping 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 insulation. Specifically, a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on an insulating layer (resin for forming an insulating layer for forming a conductor layer composition). Moreover, in the printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention also includes adhesive films, sheet laminate materials such as prepreg, solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole-filling resins, component-embedding resins, and the like. Can be used for 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 the sealing resin composition of the present invention for sealing the semiconductor chip. Cured material and. This semiconductor chip package can be manufactured by bonding a semiconductor chip to a printed wiring board.

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

Any condition that allows conductor connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the printed wiring board can be adopted as the bonding condition of the printed wiring board and the semiconductor chip. For example, conditions used in flip-chip mounting of semiconductor chips can be employed. Also, for example, the semiconductor chip and the printed wiring board may be bonded via an insulating adhesive.

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

Another example of the bonding method is a method of reflowing and bonding a semiconductor chip to a printed wiring board. The reflow conditions may range from 120.degree. C. to 300.degree.

After bonding the semiconductor chip to the printed wiring board, the semiconductor chip may be filled with a mold underfill material. As the mold underfill material, the resin composition described above may be used, 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 a semiconductor chip package according to the second embodiment, for example, a fan-out type WLP can be used.

A method for manufacturing such a semiconductor chip package includes:
(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 substrate and the temporary fixing film have been removed;
(F) forming a rewiring layer as a conductor layer on the rewiring forming layer;
(G) forming a solder resist layer on the rewiring layer;
including. Further, the method for manufacturing the semiconductor chip package includes:
(H) A step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages to individualize them.

(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.

Examples of substrates include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel and cold-rolled steel plate (SPCC); A heat-cured substrate; a substrate made of bismaleimide triazine resin such as BT resin; and the like.

Any material that can be peeled off from the semiconductor chip and that can temporarily fix the semiconductor chip can be used for the temporary fixing film. 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. Temporary fixing of the semiconductor chip can be performed using a device such as a flip chip bonder, a die bonder, or the like. The layout and the number of semiconductor chips to be arranged can be appropriately set according to the shape and size of the temporary fixing film, the target production volume of the semiconductor package, and the like. For example, the semiconductor chips may be arranged in a matrix of multiple rows and multiple columns and temporarily fixed.

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

It is preferable to form the resin composition layer by compression molding, taking advantage of the excellent compression moldability of the sealing resin composition. In the compression molding method, usually, a semiconductor chip and a resin composition are placed in a mold, and pressure and, if necessary, heat are applied to the encapsulating resin composition in the mold to form a resin composition layer covering the semiconductor chip. Form.

A specific operation of the compression molding method may be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. In addition, 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 encapsulating resin composition is attached to the lower mold together with the substrate and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped, and heat and pressure are applied to the encapsulating resin composition for compression molding.

Further, the specific operation of the compression molding method may be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. A sealing resin composition is placed on the lower mold. Also, the semiconductor chip is attached to the upper mold together with the base material and the temporary fixing film. After that, 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 encapsulating resin composition, and appropriate conditions can be adopted so as to achieve good encapsulation. For example, the temperature of the mold during molding is preferably a temperature at which the encapsulating 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 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, and preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The curing time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 5 minutes or longer, and preferably 60 minutes or shorter, more preferably 30 minutes or shorter, and particularly preferably 20 minutes or shorter. After formation of the resin composition layer, the mold is usually removed. The mold may be removed before or after heat curing 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 forming the resin composition layer are the same as the conditions for compression molding.

The resin composition layer may be formed by laminating an adhesive film and a semiconductor chip. For example, the resin composition layer can be formed on the semiconductor chip by heat-pressing the resin composition layer of the adhesive film and the semiconductor chip. Lamination of the adhesive film and the semiconductor chip can be carried out in the same manner as the lamination of the adhesive film and the interior substrate in the manufacturing method of the printed wiring board, usually 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. As a result, the semiconductor chip is sealed with the cured resin composition for sealing. The thermosetting conditions for the resin composition layer may be the same as the thermosetting conditions for the resin composition layer in the method for producing a printed wiring board. Furthermore, before thermally curing the resin composition layer, the resin composition layer may be subjected to a preheating treatment of heating at a temperature lower than the curing temperature. The treatment conditions for this preheating treatment may be the same as those for the preheating treatment in the printed wiring board manufacturing method.

(Step (D))
Step (D) is a step of peeling off the substrate and the temporary fixing film from the semiconductor chip. As for the peeling method, it is desirable to employ 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. Moreover, as a peeling method, for example, a method of irradiating the temporary fixing film with ultraviolet rays through the base material to reduce the adhesive strength of the temporary fixing film and peel it off can be used.

In the method of peeling by heating, foaming or expanding the temporary fixing film, the heating conditions are usually 100° C. to 250° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. In the method of peeling off the temporary fixing film by irradiating it with ultraviolet rays to reduce its adhesive strength, the irradiation dose of ultraviolet rays is usually 10 mJ/cm ² to 1000 mJ/cm ² .

(Step (E))
Step (E) is a step of forming a rewiring forming layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed.

Any insulating material can be used as the material of the rewiring formation layer. Among them, photosensitive resins and thermosetting resins are preferable from the viewpoint of easiness in manufacturing semiconductor chip packages. Moreover, you may use the resin composition for sealing of this invention as this thermosetting resin.

After the rewiring formation layer is formed, via holes may be formed in the rewiring formation layer for interlayer connection between the semiconductor chip and the rewiring layer.

In the method of forming a via hole when the material of the rewiring layer is a photosensitive resin, the surface of the rewiring layer is usually irradiated with an active energy ray through a mask pattern to irradiate the rewiring layer in the irradiated portion with light. Harden. Examples of active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferred. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set according to the photosensitive resin. The exposure method includes, for example, a contact exposure method in which the mask pattern is brought into close contact with the rewiring layer and exposed, and a non-contact exposure method in which the mask pattern is not brought into close contact with the rewiring layer and is exposed using parallel light rays. is mentioned.

After the rewiring layer is photo-cured, the rewiring layer is developed to remove the unexposed portions to form via holes. The development may be either wet development or dry development. The development method includes, for example, a dipping method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and the paddle method is preferable from the viewpoint of resolution.

When the material of the rewiring formation layer is a thermosetting resin, the method of forming via holes includes, for example, laser irradiation, etching, mechanical drilling, and the like. Among them, laser irradiation is preferable. Laser irradiation can be performed using an appropriate laser processing machine using a light source such as a carbon dioxide laser, a UV-YAG laser, an excimer laser, or the like.

Although the shape of the via hole is not particularly limited, it is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, still more 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 means the diameter of the opening of the via hole on the surface of the rewiring layer.

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

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

Moreover, in the step (G), a bumping process for forming bumps may be performed as necessary. Bumping can be performed by a method such as solder balls or solder plating. Formation of via holes in the bumping process can be performed in the same manner as in step (E).

The method for manufacturing a semiconductor chip package may include step (H) in addition to steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into pieces. 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, the semiconductor chip package of the second embodiment, in which the rewiring formation layer or the solder resist layer is formed from the cured product of the resin composition of the present invention. is.

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

Adhesive films and prepregs shown below are preferable as the sheet-like laminate material.

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

The thickness of the resin composition layer is preferably 50 μm or less, more It is preferably 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 a 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, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. 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 copper foil and aluminum foil, with copper foil being preferred. 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 other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1" manufactured by Lintec Co., Ltd., "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

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

In one embodiment, the adhesive film may further contain optional layers as needed. Examples of such an optional layer include a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. 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, the surface of the resin composition layer can be prevented from being dusted or scratched.

For the adhesive film, for example, a resin varnish is prepared by dissolving a resin composition in an organic solvent, the resin varnish is applied onto a support using a die coater or the like, and dried to form a resin composition layer. It can be manufactured by

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid esters 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. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it varies depending 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 the organic solvent, drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes The resin composition 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, a prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

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

A prepreg can be manufactured by a known method such as a hot melt method or a solvent method.

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

In the present invention, which uses a resin composition containing a combination of components (A), (B), (C), and (D) in a specific content, warping can be suppressed, and under high temperature and high humidity, Since a cured product having a low dielectric loss tangent can be obtained even after being left for a long time, it is possible to realize a sheet-like laminate material that is extremely useful in the production of printed wiring boards.

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 (for a printed wiring board). for interlayer insulating layers of wiring boards).

<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.

A printed wiring board can be produced, for example, using the above-described adhesive film by a method including the following steps (I) and (II).
(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, thermosetting) the resin composition layer to form an insulating layer process

The "inner layer substrate" used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" as used in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

The lamination of the inner layer substrate and the adhesive film can be performed, for example, by thermocompression bonding the adhesive film to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the adhesive film to the inner layer substrate (hereinafter also referred to as “thermocompression member”) include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of directly pressing the thermocompression member onto the adhesive film, it is preferable to press the adhesive film through an elastic material such as heat-resistant rubber so that the adhesive film can sufficiently follow the unevenness of the surface of the inner layer substrate.

Lamination of the inner layer substrate and the adhesive film may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.

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

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

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

For example, although the thermosetting conditions for the resin composition layer vary depending on the type of resin composition, etc., 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 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.

Before thermosetting 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 cured at a temperature of 50° C. or higher and lower than 120° C., preferably 60° C. or higher and lower than 115° C., more preferably 70° C. or higher and lower than 110° C. Minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, more preferably 15 minutes to 100 minutes, may be preheated.

When manufacturing a printed wiring board, (III) the step of drilling holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. 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 step ( It may be carried out between IV) and step (V). If necessary, the steps (II) to (V) of forming the insulating layer and the conductor layer 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 in the case of using an adhesive film.

Step (III) is a step of making holes in the insulating layer, whereby holes such as via holes and through holes 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 dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Smear is usually also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order.

The swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, more preferably sodium hydroxide solutions and potassium hydroxide solutions. 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 the swelling liquid at 30.degree. C. to 90.degree. C. for 1 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 in the roughening treatment is not particularly limited, but 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 with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 to 30 minutes. Further, the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.

Moreover, as a neutralization liquid used for the roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. can be mentioned.

The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.

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

Step (V) is a step of forming a conductor layer, in which 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 conductor layer contains 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. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred. A metal layer is more preferred.

The conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. 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 nickel-chromium alloy.

The thickness of the conductor layer is generally between 3 μm and 35 μm, preferably between 5 μm and 30 μm, depending on the desired printed wiring board design.

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method. An example of forming a conductor layer by a semi-additive method is shown below.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

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

A metal foil can be manufactured by a known method such as an electrolysis method or a rolling method. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd., and the like.

When producing a printed wiring board using the resin composition of the present invention containing a combination of components (A), (B), (C), and (D) in a specific content, the conductor layer is Regardless of whether it is formed by plating or by 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>
A 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 semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

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. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, 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. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. Here, "a mounting method using a build-up layer without bumps (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

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

First, the measurement/evaluation methods in the evaluation of physical properties in this specification will be described.

<Evaluation of warpage>
On a 12-inch silicon wafer, the resin compositions produced in the following Examples and Comparative Examples were compression-molded using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes). , a resin composition layer having a thickness of 300 μm was formed. After that, the resin composition layer was thermally cured by heating at 180° C. for 90 minutes. As a result, a sample substrate including a silicon wafer and a cured product layer of the resin sealing resin composition was obtained. Using a shadow moire measuring device (“Thermoire AXP” manufactured by Akorometrics), the amount of warpage of the sample substrate at 25° C. was measured. The measurement was performed in accordance with JEITA EDX-7311-24 of the Japan Electronics and Information Technology Industries Association standard. Specifically, a virtual plane calculated by the method of least squares of all data of 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 direction perpendicular to the reference plane was obtained as the amount of warpage. A warpage amount of less than 2 mm was evaluated as "◯", a warpage amount of 2 mm or more and less than 3 mm was evaluated as "Δ", and a warp amount of 3 mm or more was evaluated as "x".

<Dielectric loss tangent after high temperature and high humidity environment test (HAST)>
The resin compositions produced in the following examples and comparative examples were placed on a SUS plate whose surface had been subjected to mold release treatment, using a compression molding device (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 product of the resin composition. After that, 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 HAST was cut into a test piece having a width of 2 mm and a length of 80 mm, and was measured using a cavity resonator perturbation method dielectric constant measurement device CP521 manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technologies. was used to measure the dielectric loss tangent (tan δ) at a measurement frequency of 5.8 GHz by the cavity resonance method. Two test pieces were measured, 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>
Glycidylamine type epoxy resin (ADEKA "EP3980S", epoxy equivalent 115 g / eq.) 3 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Corporation "630LSD", epoxy equivalent 95 g / eq.) 6 parts, polyvalent glycidyl Compound (Showa Denko "BATG", epoxy equivalent 119 g / eq.) 4 parts, bisphenol A type epoxy resin (DIC "EXA-850CRP", epoxy equivalent 170 to 175 g / eq.) 4 parts, phenolic curing agent (Meiwa Kasei "MEH-8000H") 1 part, spherical silica treated with KBM403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 4.8 μm, maximum cut diameter 20 μm , a specific surface area of 3.9 m ² /g) 83 parts, and 0.4 parts of 2-ethyl-4-methylimidazole (“2E4MZ” manufactured by Shikoku Kasei Co., Ltd.) are uniformly dispersed using a mixer to form a resin composition. Obtained.

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

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

<Example 4>
In the same manner as in Example 1, except that 1 part of the phenolic curing agent ("MEH-8000H" manufactured by Meiwa Kasei) was changed to 1 part of the amine curing agent ("Kayabond C-200S" manufactured by Nippon Kayaku Co., Ltd.). A resin composition was obtained.

<Example 5>
Glycidylamine type epoxy resin (ADEKA "EP3980S", epoxy equivalent 115 g / eq.) 2 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Corporation "630", epoxy equivalent 95 g / eq.) 3 parts, polyvalent glycidyl Compound (Showa Denko "BATG", epoxy equivalent 119 g / eq.) 1 part, bisphenol A epoxy resin (DIC "EXA-850CRP", epoxy equivalent 170 to 175 g / eq.) 6 parts, acid anhydride Spherical silica (average particle size Diameter 4.8 μm, maximum cut diameter 20 μm, specific surface area 3.9 m ² /g) 83 parts and 0.1 part of 2-ethyl-4-methylimidazole ("2E4MZ" manufactured by Shikoku Kasei Co., Ltd.) were uniformly mixed using a mixer. to obtain a resin composition.

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

<Comparative Example 2>
Glycidylamine type epoxy resin (manufactured by Mitsubishi Chemical Corporation "630", epoxy equivalent 95 g / eq.) 6 parts, polyvalent glycidyl compound (manufactured by Showa Denko "BATG", epoxy equivalent 119 g / eq.) 7 parts, bisphenol A type Epoxy resin (DIC "EXA-850CRP", epoxy equivalent 170 to 175 g / eq.) 1 part, phenolic curing agent (Meiwa Kasei "MEH-8000H") 4 parts, KBM403 (3-glycidoxypropyltri Methoxysilane, Shin-Etsu Chemical Co., Ltd.) treated spherical silica (average particle diameter 4.8 μm, maximum cut diameter 20 μm, specific surface area 3.9 m ² / g) 83 parts, 2-ethyl-4-methylimidazole (Shikoku 0.4 part 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 Examples and Comparative Examples.

From the above results, by including the (A) component, (B) component, (C) component and (D) component in a specific content in the resin composition, warping can be suppressed and It can be seen that a cured product with a low dielectric loss tangent can be obtained even after being placed for a long time.

Claims (10)

(A) a glycidylamine type epoxy resin,
(B) the following formula (B-1)

[In formula (B-1),
Each n' independently represents an integer of 0 to 3.
m' represents an integer of 1 to 3;
Each R ²¹ independently represents a monovalent hydrocarbon group.
R ²² represents a hydrogen atom or a monovalent to trivalent hydrocarbon group. ]
A polyvalent glycidyl compound represented by
(C) a curing agent, and (D) a resin composition containing an inorganic filler,
When the non-volatile component in the resin composition is 100% by mass, the content of component (A) is 3% by mass to 15% by mass,
A resin composition in which the content of the component (B) is 0.2% by mass to 6.5% by mass when the non-volatile component in the resin composition is 100% by mass. 2. The resin composition according to claim 1, wherein the content of component (A) is 5% by mass to 10% by mass, based on 100% by mass of non-volatile components in the resin composition. 3. The resin composition according to claim 1, wherein component (C) is selected from the group consisting of phenolic curing agents, acid anhydride curing agents, amine curing agents, and imidazole curing agents. 4. The resin composition according to any one of claims 1 to 3, wherein the content of component (D) is 80% by mass or more when the non-volatile 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 used for encapsulating semiconductor chips. A sheet-like laminate material containing the resin composition according to any one of claims 1 to 4. A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 4. A semiconductor chip package comprising a cured product of the resin composition according to any one of claims 1 to 4. A semiconductor device comprising a cured product of the resin composition according to any one of claims 1 to 4.