JP2019085493A - Resin composition - Google Patents

Abstract

To provide a resin composition that makes it possible to obtain a cured product that has a low linear thermal expansion coefficient, can suppress warpage, and can prevent the occurrence of a flow mark.SOLUTION: The present invention provides a resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a compound having a rotaxane structure, and (D) inorganic filler.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition. Furthermore, the present invention relates to a circuit board and a semiconductor chip package using a resin composition.

  In recent years, the demand for small high-performance electronic devices such as smartphones and tablet devices is increasing, and accordingly, the insulating layer for semiconductor chip package used for these small-sized electronic devices is also required to be further enhanced in function . As such an insulating layer, for example, one formed by curing a resin composition is known (see, for example, Patent Document 1).

Japanese Patent Publication No. 2016-534164 gazette

In recent years, a smaller semiconductor chip package has been required, and a thinner insulating layer used for the semiconductor chip package is required. For this reason, development of the insulating layer in which a linear thermal expansion coefficient (Coefficient of Thermal Expansion. CTE, and a thermal expansion coefficient may be called) is low, and can control curvature is desired.
In order to suppress the warpage, it is conceivable to add a liquid component and a soft component to the resin composition, but in this case, the flow mark tends to be generated, and for the compatibility of the suppression of the warpage and the suppression of the flow mark There are still issues remaining.

  Moreover, using the resin composition used to form an insulating layer as a sealing material of a semiconductor chip package is also considered. The above problems also occur similarly when the resin composition is used as a sealing material of a semiconductor chip package.

  The present invention has been made in view of the above problems, and has a low linear thermal expansion coefficient, can suppress warpage, and can obtain a cured product capable of suppressing generation of a flow mark; A resin sheet having a resin composition layer containing the resin composition; a circuit board including an insulating layer formed of a cured product of the resin composition; and a semiconductor chip package including the cured product of the resin composition; Intended to provide.

As a result of intensive studies to solve the above problems, the present inventor has found that (A) an epoxy resin, (B) a curing agent, (C) a compound having a rotaxane structure, and (D) a resin containing an inorganic filler in combination. It has been found that the above-mentioned problems can be solved by the composition, and the present invention has been completed.
That is, the present invention includes the following.

[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) a compound having a rotaxane structure, and (D) an inorganic filler.
[2] The resin composition according to [1], wherein the component (C) is a polyrotaxane.
[3] The resin according to [1] or [2], wherein the content of the component (C) is 0.1 mass% or more and 10 mass% or less when the nonvolatile component of the resin composition is 100 mass%. Composition.
[4] The resin composition according to any one of [1] to [3], wherein the component (C) is particulate.
[5] The resin composition according to any one of [1] to [4], wherein the average particle diameter of the component (C) is 100 nm or more and 20000 nm or less.
[6] The resin composition according to any one of [1] to [5], wherein the component (C) contains a cyclic molecule containing cyclodextrins.
[7] The resin composition according to any one of [1] to [6], wherein the component (C) comprises an axial molecule containing a polyethylene glycol chain.
[8] The resin composition according to any one of [1] to [7], wherein the weight average molecular weight of the axial molecule in the component (C) is 3,000 or more and 100,000 or less.
[9] The inclusion amount of the cyclic molecule in the component (C) is 10% or more and 90% or less, where the amount of the cyclic molecule to be maximally included in one axial molecule is 100%, [1] The resin composition in any one of [8].
[10] The resin composition according to any one of [1] to [9], wherein the content of the component (D) is 50% by mass or more when the nonvolatile component of the resin composition is 100% by mass.
[11] The resin composition according to any one of [1] to [10], wherein the component (B) contains any of a phenolic curing agent and an acid anhydride curing agent.
[12] The resin composition according to any one of [1] to [11], which is a resin composition for encapsulating a semiconductor or an insulating layer.
[13] The resin composition according to any one of [1] to [12], which is a liquid resin composition.
[14] A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [13].
[15] A semiconductor chip package comprising the circuit board according to [14] and a semiconductor chip mounted on the circuit board.
[16] A semiconductor chip package, comprising: a semiconductor chip; and a cured product of the resin composition according to any one of [1] to [13] for sealing the semiconductor chip.

  According to the present invention, a resin composition having a low linear thermal expansion coefficient, capable of suppressing warpage, and capable of obtaining a cured product capable of suppressing generation of a flow mark; formed by the cured product of the above resin composition It is possible to provide a circuit board including the insulating layer; and a semiconductor chip package including the cured product of the resin composition described above.

FIG. 1 is a cross-sectional view schematically showing a Fan-out type WLP as an example of a semiconductor chip package according to a second embodiment of the present invention.

  Hereinafter, the present invention will be described in detail by way of embodiments and exemplifications. However, the present invention is not limited to the embodiments and exemplifications listed below, and can be implemented with arbitrary modifications without departing from the scope of the claims of the present invention and the equivalents thereof.

[1. Resin composition]
The resin composition of the present invention comprises (A) an epoxy resin, (B) a curing agent, (C) a compound having a rotaxane structure, and (D) an inorganic filler. The resin composition has a low coefficient of linear thermal expansion and a warp due to the combination of the (A) epoxy resin, (B) curing agent, (C) compound having rotaxane structure, and (D) inorganic filler. It is possible to obtain the desired effect of the present invention that it is possible to obtain a cured product capable of suppressing the generation of flow marks and suppressing the generation of The cured product of this resin composition can be preferably used as an insulating layer and a sealing material of a semiconductor chip package, taking advantage of its excellent properties.

  In addition, the above resin composition may further contain optional components in combination with (A) epoxy resin, (B) curing agent, (C) compound having rotaxane structure, and (D) inorganic filler. Good. As an arbitrary component, (E) hardening accelerator etc. are mentioned, for example.

[2. (A) Epoxy resin]
The resin composition contains (A) an epoxy resin. (A) As an epoxy resin, 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, trisphenol type Epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin Cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin Heterocyclic epoxy resins, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. Among them, glycidyl amine type epoxy resin, alicyclic epoxy resin, naphthylene ether type epoxy resin, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable. The epoxy resin may be used alone or in combination of two or more.

  The (A) epoxy resin preferably has two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups in one molecule. Among them, the resin composition is an epoxy resin which is liquid at a temperature of 20 ° C. (hereinafter also referred to as “liquid epoxy resin”) and an epoxy resin which is solid at a temperature of 20 ° C. (hereinafter also referred to as “solid epoxy resin”). It is preferable to include in combination. The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule. The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule.

  As liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, ester skeleton Aliphatic epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin, aliphatic epoxy resin, and epoxy resin having butadiene structure are preferable, and aliphatic epoxy resin, bisphenol A type epoxy resin And bisphenol F-type epoxy resin are more preferable.

  Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US" manufactured by Mitsubishi Chemical Corp., "jER828EL", "825", "epicoat" “828 EL” (bisphenol A epoxy resin), “jER 807”, “1750” (bisphenol F epoxy resin), “jER 152” (phenol novolac epoxy resin), “630”, “630 LSD” (glycidyl amine epoxy resin) , “ZX1059” (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel Sumikin Chemical Co., Ltd., “EX-721” manufactured by Nagase ChemteX (glycidyl ester epoxy resin), manufactured by Daicel "CEL 202 P "(alicyclic epoxy resin having an ester skeleton)," PB-3600 "(epoxy resin having a butadiene structure)," ZX1658 "manufactured by Nippon Steel Sumikin Chemical Co., Ltd.," ZX1658GS "(liquid 1,4-glycidyl cyclohexane type Epoxy resin), "630LSD" (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Corp., "EXA-850 CRP" manufactured by DIC (bisphenol A epoxy resin), "YED-216D" manufactured by Mitsubishi Chemical Corp. (aliphatic) Epoxy resin), "EP-3950S" manufactured by ADEKA, "EP-3980S" (glycidyl amine type epoxy resin); "ELM-100H" manufactured by Sumitomo Chemical (glycidyl amine type epoxy resin), etc. may be mentioned. These may be used singly or in combination of two or more.

  As solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl Type epoxy resin, naphthalene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin is preferable, and bixylenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF Type epoxy resin, and naphthalene ether type epoxy resin are more preferable.

  Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin) manufactured by DIC; “HP-4700” manufactured by DIC, “HP-4710” (naphthalene type tetrafunctional epoxy resin); “N-690” (cresol novolac epoxy resin); “N-695” (cresol novolac epoxy resin) manufactured by DIC; “HP-7200” (dicyclopentadiene type epoxy resin) manufactured by DIC; "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000L" manufactured by DIC Corporation, “HP 6000” (Naphthylene Ether Type Epoxy Resin); “EPPN-502H” manufactured by Nippon Kayaku Co., Ltd. Phenolic epoxy resin); "NC7000L" (naphthol novolac epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl epoxy resin) manufactured by Nippon Kayaku Co., Ltd. “ESN 475 V” (naphthalene type epoxy resin) manufactured by Nippon Steel Sumikin Chemical Co., Ltd. “ESN 485” (naphthol novolac type epoxy resin) manufactured by Nippon Steel Sumikin Chemical Co., Ltd. “YX4000H”, “YX 4000”, “YL 6121” manufactured by Mitsubishi Chemical Co. (Biphenyl type epoxy resin); "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX 8800" manufactured by Mitsubishi Chemical Co., Ltd. (anthracene type epoxy resin); "PG-100" manufactured by Osaka Gas Chemical Co., "CG-500"; Mitsubishi Michal's "YL 7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical's "YL 7800" (fluorene type epoxy resin); Mitsubishi Chemical's "jER1010" (solid bisphenol A type epoxy resin); Company-made "jER1031S" (tetraphenyl ethane type epoxy resin) etc. are mentioned. These may be used alone or in combination of two or more.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (A), their mass ratio (liquid epoxy resin: solid epoxy resin) is 1: 0.01 to 1:20 in mass ratio A range is preferred. By setting the ratio of the liquid epoxy resin to the solid epoxy resin in this range, i) adequate tackiness is provided, ii) sufficient flexibility is obtained, and the handleability is improved, and iii The effect is obtained that a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of the above i) to iii), the mass ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.01 to 1:15 by mass ratio Is more preferable, and the range of 1: 0.01 to 1: 1 is more preferable.

The content of the component (A) in the resin composition is preferably 1 mass when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. % Or more, more preferably 5% by mass or more, further preferably 7% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass unless otherwise specified.

  The epoxy equivalent of the component (A) is preferably 50 to 5,000, more preferably 50 to 3,000, still more preferably 80 to 2,000, and still more preferably 110 to 1,000. By being in this range, the crosslink density of the cured product is sufficient, and an insulating layer with a small surface roughness can be provided. In addition, an epoxy equivalent can be measured according to JISK7236, and is a mass of resin containing an epoxy group of 1 equivalent.

  The weight average molecular weight of the component (A) is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. Here, the weight average molecular weight of an epoxy resin is a weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

[3. (B) Hardening agent]
The resin composition contains a curing agent as component (B). The curing agent (B) usually has a function of reacting with the (A) epoxy resin to cure the resin composition. The curing agent (B) may be used alone or in combination of two or more at an arbitrary ratio.

  As the curing agent (B), a compound capable of curing the resin composition by reacting with an epoxy resin can be used. For example, an acid anhydride curing agent, a phenol curing agent, an active ester curing agent, Examples thereof include cyanate ester-based curing agents, benzoxazine-based curing agents, and carbodiimide-based curing agents. Among them, acid anhydride type curing agents and phenol type curing agents are preferable from the viewpoint of obtaining the effects of the present invention remarkably.

  The acid anhydride curing agent includes a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic acid Anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride Mellitic acid, pyromellitic anhydride, bensophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'- Diphenyl sulfone tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexene Hydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione, ethylene glycol bis (anhydrotrimellitate), styrene and maleic acid And polymer-type acid anhydrides such as styrene-maleic acid resins copolymerized with

  As a commercial item of an acid anhydride system hardening agent, "MH-700" by Shin Nippon Rika Co., Ltd., etc. are mentioned.

  Examples of the phenol-based curing agent include curing agents having one or more, preferably two or more hydroxyl groups bonded to an aromatic ring (benzene ring, naphthalene ring, etc.) in one molecule. Among them, compounds having a hydroxyl group bonded to a benzene ring are preferable. Further, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure is preferable. Furthermore, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. In particular, from the viewpoint of highly satisfying heat resistance, water resistance and adhesion, a triazine skeleton-containing phenol novolac curing agent is preferred.

  Commercially available products of phenolic curing agents and naphtholic curing agents include “MEH-7700”, “MEH-7810”, “MEH-7851”, “MEH-8000H” manufactured by Meiwa Kasei Co., Ltd .; manufactured by Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”; “SN-170”, “SN-180,” “SN-190,” “SN-475,” “SN-485,” “SN-170”, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. -495 "," SN-495 V "," SN-375 "," SN-395 ";" TD-2090 "," TD-2090-60M "," LA-7052 "," LA-7054 "manufactured by DIC Corporation. “LA-1356”, “LA-3018”, “LA-3018-50P”, “EXB-9500”, “HPC-9500”, “KA-1160”, “KA-1163”, “KA-1165” " Gun Ei Chemical Industry Co., Ltd. of "GDP-6115L", "GDP-6115H", "ELPC75", and the like.

  Examples of the active ester curing agent include curing agents having one or more active ester groups in one molecule. Among them, as an active ester curing agent, two or more ester groups having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. in one molecule The compound which it has is preferable. The active ester curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, active ester-based curing agents obtained from carboxylic acid compounds and hydroxy compounds are preferable, and active ester-based curing agents obtained from carboxylic acid compounds and phenol compounds and / or naphthol compounds are more preferable. .

  Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid.

  As a phenol compound or naphthol compound, for example, hydroquinone, resorcine, 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, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compounds, phenol novolac and the like can be mentioned. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensation of two molecules of phenol with one molecule of dicyclopentadiene.

  Preferred specific examples of the active ester-based curing agent include 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 compound of phenol novolac, and a benzoyl compound of phenol novolac And active ester compounds. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" represents a bivalent structure consisting of phenylene-dicyclopentylene-phenylene.

  As a commercial item of an active ester type curing agent, "EXB9451", "EXB 9460", "EXB 9460S", "HPC-8000", "HPC-8000H" and "HPC-8000H" as an active ester compound containing a dicyclopentadiene type diphenol structure. HPC-8000-65T "," HPC-8000H-65TM "," EXB-8000L "," EXB-8000L-65TM "," EXB-8150-65T "(manufactured by DIC); as an active ester compound containing a naphthalene structure "EXB9416-70BK" (made by DIC); "DC 808" (made by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac; "YLH1026" (Mitsubishi Chemica) as an active ester compound containing a benzoyl compound of phenol novolac Company); "DC 808" (Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is an acetylated product of phenol novolak; "YLH1026" (Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is a benzoyl compound of phenol novolac "YLH1030" (made by Mitsubishi Chemical Co., Ltd.), "YLH1048" (made by Mitsubishi Chemical Co., Ltd.);

  As a cyanate ester-based curing agent, for example, bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylene bis (2,6-dimethylphenyl cyanate), 4,4 '-Ethylidene diphenyl dicyanate, hexafluoro bisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1, 1-bis (4- cyanate phenyl methane), bis (4- cyanate 3,5- dimethyl) A bifunctional cyanate resin such as phenyl) methane, 1,3-bis (4-cyanatophenyl-1- (methylethylidene)) benzene, bis (4-cyanatophenyl) thioether, and bis (4-cyanatophenyl) ether; Phenolic novolak and Polyfunctional cyanate resin derived from resol novolac; prepolymer these cyanate resin is partially triazine of; and the like. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins) manufactured by Ronza Japan Co., Ltd .; "ULL-950S" (polyfunctional cyanate ester resins); BA 230 ′ ′, “BA 230 S 75” (a prepolymer in which part or all of bisphenol A dicyanate is triazinated to trimer), and the like.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Highpolymer Co., Ltd. and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

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

  The content of the component (B) is preferably 1% by mass or more, more preferably 2% by mass, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining the desired effects of the present invention remarkably. The content is more preferably 3% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.

  The quantitative ratio of the (A) epoxy resin to the (B) curing agent is a ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent] 1: 1: 1 to 1: The range of 2 is preferable, 1: 0.05 to 1: 3 is more preferable, and 1: 0.1 to 1: 1.5 is more preferable. Here, the reactive group of the curing agent is an active hydroxyl group or the like, which differs depending on the type of the curing agent. Further, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the mass of the solid content of each epoxy resin by the epoxy equivalent, for all the epoxy resins, and the total number of reactive groups of the curing agent is It is the value which totaled the value which remove | divided the solid content mass of each hardening | curing agent by reaction group equivalent for all the hardening | curing agents. By setting the ratio of the epoxy resin to the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.

[4. (C) Compound Having Rotaxane Structure]
The resin composition contains a compound having a rotaxane structure as the component (C). The rotaxane structure is a structure having a cyclic molecule, a linear axial molecule which is included so as to penetrate the cyclic molecule, and a blocking group which blocks the terminal of the axial molecule so that the cyclic molecule is not removed. The rotaxane structure is considered to be flexible since cyclic molecules and axial molecules are not bonded. As a result, by including the compound having the rotaxane structure in the resin composition, it is possible to reduce the viscosity of the resin composition, and it is possible to further suppress the warpage of the cured product of the resin composition.

  The component (C) is not particularly limited as long as it has a rotaxane structure, but is preferably a polyrotaxane having a plurality of at least one of a cyclic molecule and a shaft molecule, and is more preferably a polyrotaxane having a plurality of cyclic molecules. preferable. The number (inclusion amount) of cyclic molecules in the polyrotaxane is not particularly limited as long as the number of cyclic molecules is 2 or more. For example, one axial molecule is penetrated by a plurality of cyclic molecules. When inclusion is performed, the amount of maximum inclusion of cyclic molecules in one axial molecule (maximum inclusion amount) is 100%, preferably 10% or more, more preferably 15% or more, still more preferably 20% or more Preferably it is 90% or less, More preferably, it is 85% or less, More preferably, it is 80% or less. By making the number (inclusion amount) of cyclic molecules within such a range, it is possible to further suppress the warpage of the cured product of the resin composition. The amount of inclusion can be determined by the length of the axial molecule and the thickness of the cyclic molecule. For example, when the axial molecule is polyethylene glycol and the cyclic molecule is α-cyclodextrin molecule, the maximum inclusion amount is experimentally determined (see Macromolecules 1993, 26, 5698-5703).

  As an axial molecule in the rotaxane structure, a linear molecule having a molecular weight of 10000 or more and capable of being chemically modified at the terminal with a blocking group can be used. The term "linear" means that the molecule is substantially linear, and the axial molecule may have a branched chain, as long as rotation or movement of the cyclic molecule penetrated by the axial molecule is possible. . As an axial molecule, for example, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose (poly) (meth) acrylate resin, polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethylene imine, casein , Gelatin, starch, polyolefin, polyester, polyvinyl chloride, polystyrene, copolymer such as acrylonitrile-styrene copolymer, acrylic resin, polycarbonate, polyurethane, polyvinyl butyral, polyisobutylene, polytetrahydrofuran, polyamide, polyimide, polydiene, polydiene Siloxane, polyurea, polysulfide, polyphosphazene, polyketone, polyphenylene, poly B olefins and their derivatives, and the like. Among these, polyethylene glycol chains are preferably used. Two or more of these may be mixed in the polyrotaxane.

  The length of the axial molecule is not particularly limited as long as it can rotate or move the cyclic molecule. The length of the axial molecule can be expressed using weight average molecular weight. The weight average molecular weight of the axial molecule is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, preferably 100,000 or less, more preferably 90,000 or less, still more preferably 85,000 or less. By making the weight average molecular weight of the axial molecule within such a range, it is possible to further suppress the warpage of the cured product of the resin composition. The weight average molecular weight of the axial molecule is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

  The axial molecule generally has a structure in which a molecule containing a blocking group is reacted and bound to the functional group of the molecule having functional groups at both ends. As a functional group, an amido group, a hydroxyl group, a carboxyl group, an acryl group, a methacryl group, an epoxy group, a vinyl group etc. are mentioned preferably, for example.

  The cyclic molecule in the rotaxane structure is a cyclic molecule that can be clathrated in a state in which the axial molecule is penetrated, and has at least one reactive group (functional group) so as to be able to react with (B) a curing agent Molecules can be used. A cyclic molecule is a molecule that is substantially cyclic, and "substantially cyclic" is meant to include those that are not completely ring-closed, and one end of the letter "C" and the other end are bonded It is a concept that includes those with no overlapping spiral structure. Examples of cyclic molecules include cyclodextrins, crown ethers, cryptands, macrocyclic amines, calixarenes, cyclophanes and the like. Among these, cyclodextrins are preferable. Two or more of these may be mixed in the polyrotaxane.

  Examples of cyclodextrins include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, dimethyl cyclodextrin and glucosyl cyclodextrin, their derivatives or modified products, and the like.

  The cyclic molecule preferably contains a reactive group. Examples of the reactive group include a hydroxyl group, a carboxyl group, an acryl group, a methacryl group, an epoxy group, a vinyl group and the like, and among them, a hydroxyl group is preferable. When the cyclic molecule has a reactive group, it is possible to crosslink the cyclic molecules or the component (C) with the epoxy resin (A) via the curing agent (B). Also, the reactive group of one cyclic molecule and the reactive group of the other cyclic molecule may be crosslinked. As a result, it is possible to suppress the warpage of the cured product of the resin composition. The reactive group may be present singly or in combination of two or more.

  The reactive group may not be directly attached to the cyclic molecule. For example, when the cyclic molecule is cyclodextrin, the hydroxyl group present in the cyclodextrin itself is a reactive group, and when a hydroxypropyl group is added to the hydroxyl group, the hydroxyl group of the hydroxypropyl group is also a reactive group. Furthermore, when ring-opening polymerization of ε-caprolactone is performed via a hydroxyl group of a hydroxypropyl group and a caprolactone chain is included, the hydroxyl group located at the opposite end of the polyester moiety in the caprolactone chain is also a reactive group.

  The reactive group of the cyclic molecule may have one, or two or more, per cyclic molecule.

  The weight average molecular weight of the cyclic molecule is preferably 5,000 or more, more preferably 6,000 or more, still more preferably 7,000 or more, preferably 1,500,000 or less, more preferably 1,400,000 or less, still more preferably 135,000 or less. By setting the weight average molecular weight of the cyclic molecule within such a range, it is possible to further suppress the warpage of the cured product of the resin composition. The weight average molecular weight of the cyclic molecule is a weight average molecular weight in terms of polystyrene, which is measured by gel permeation chromatography (GPC).

  The blocking group in the rotaxane structure is not particularly limited as long as it is a structure having such a bulk that the cyclic molecule is not removed. Examples of blocking groups include cyclodextrin group, adamantane group, dinitrophenyl group, trityl group and the like. Among them, an adamantane group is preferred. These may be possessed alone in the polyrotaxane, or may be possessed in two or more.

  The weight average molecular weight of the entire compound having a rotaxane structure (C) is preferably 10000 or more, more preferably 15000 or more, still more preferably 20000 or more, preferably 1.500000 or less, more preferably 1400000 or less, further preferably 1350000 It is below. By making the weight average molecular weight of the whole compound which has (C) rotaxane structure into such a range, it becomes possible to control more curvature of a hardened material of a resin composition. The weight average molecular weight of the whole compound which has (C) rotaxane structure is a weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) method.

  The hydroxyl value of the compound having a rotaxane structure (C) is preferably 45 mg KOH / g or more, more preferably 50 mg KOH / g or more, still more preferably 55 mg KOH / g or more, preferably 120 mg KOH / g or less, more preferably 115 mg KOH / G or less, more preferably 110 mg KOH / g or less. By setting the hydroxyl value within such a range, the reaction with the reactive group possessed by the (A) epoxy resin, the (B) curing agent, and the other cyclic molecule becomes easier. The hydroxyl value can be measured according to JIS K 0070.

  The compound (C) having a rotaxane structure may be liquid, but is preferably contained in the form of particles in the resin composition. The particulate component (C) can be easily dispersed and can further reduce the viscosity of the resin composition.

  The average particle diameter of the compound (C) having a rotaxane structure is preferably 100 nm or more, more preferably 500 nm or more, still more preferably 800 nm or more, preferably 50000 nm or less, more preferably 40000 nm or less, still more preferably 30000 nm or less is there. The compound having a (C) rotaxane structure having such an average particle diameter is easily dispersed uniformly in the resin composition, and the viscosity of the resin composition tends to be reduced. The average particle size can be measured by the same method as the measurement of the average particle size in (D) inorganic filler described later.

  The compound (C) having a rotaxane structure can be synthesized, for example, by the method described in WO 01/83566, JP-A 2005-154675, Patent 4482633, and the like.

  A commercially available product may be used as the compound (C) having a rotaxane structure. As commercially available products, for example, “SH2400B-007”, “SH1310P”, “Cerm super polymer A 1000” and the like manufactured by Advanced Soft Materials Co., Ltd. can be used.

  The content of the compound having a rotaxane structure (C) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 100% by mass of the nonvolatile component in the resin composition. It is 0.3% by mass or more, preferably 10% by mass or less, more preferably 9% by mass or less, still more preferably 8% by mass or less, 5% by mass or less, or 3% by mass or less. By setting the content of the compound having a rotaxane structure (C) in such a range, it is possible to reduce the viscosity of the resin composition, and it is possible to suppress the warpage of the cured product of the resin composition. .

[5. (D) Inorganic filler]
The resin composition contains an inorganic filler as the component (D). (D) By using the inorganic filler, the linear thermal expansion coefficient of the cured product of the resin composition can be reduced, and warpage can be suppressed.

  (D) An inorganic compound is used as a material of an inorganic filler. (D) As the material of the inorganic filler, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, 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 And zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferable from the viewpoint of significantly achieving the desired effects of the present invention. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Moreover, spherical silica is preferable as silica. The (D) inorganic filler may be used singly or in combination of two or more at an arbitrary ratio.

  Usually, the (D) inorganic filler is contained in the form of particles in the resin composition. The average particle diameter of the (D) inorganic filler is preferably 0.1 μm or more, more preferably 0.2 μm or more, particularly preferably 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 1.0 μm or more And preferably 10 μm or less, more preferably 8.0 μm or less, and particularly preferably 7.0 μm or less. When the average particle diameter of the (D) inorganic filler is in the above range, the filling property of the (D) inorganic filler in the resin composition is enhanced, and the desired effect of the present invention can be significantly obtained. In particular, when the average particle diameter of the (D) inorganic filler is at least the lower limit of the above range, the compression moldability of the resin composition can be effectively enhanced, and the flow mark can be reduced. In addition, when the average particle diameter of the (D) inorganic filler is in the above range, the surface roughness of the insulating layer can usually be lowered when the insulating layer is formed of a cured product of the resin composition.

  (D) The average particle diameter of particles such as an inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of particles is created on a volume basis by a laser diffraction scattering type particle size distribution measuring device, and the average particle size can be measured as a median diameter from the particle size distribution. As the measurement sample, one in which particles are dispersed in a solvent such as water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by Horiba, Ltd. can be used.

  As the (D) inorganic filler as described above, for example, “ST7030-20” manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; “MSS-6” manufactured by Ryumori Co., Ltd. “AC-5V”; manufactured by Nippon Steel Sumikin Materials Co., Ltd. SP60-05 "," SP 507-05 ";" YC100C "," YA050C "," YA050C-MJE "," YA010C ", manufactured by Admatechs," UFP-30 "," SFP-130MC "," FB, "manufactured by Denka -7SDC "," FB-5SDC "," FB-3SDC ";" Sylfil NSS-3N "manufactured by Tokuyama," Sylfil NSS-4N "," Sylfil NSS-5N ";" SC2500SQ "manufactured by Admatechs," SO -C4 "," SO-C2 "," SO-C1 "," FE9 "etc. is mentioned.

  The (D) inorganic filler is preferably surface-treated with a suitable surface treatment agent. The surface treatment can improve the moisture resistance and the dispersibility of the (D) inorganic filler. As a surface treatment agent, for example, a fluorine-containing silane coupling agent, an aminosilane based coupling agent, an epoxysilane based coupling agent, a mercaptosilane based coupling agent, a silane based coupling agent, an alkoxysilane compound, an organosilazane compound, a titanate The coupling agent etc. are mentioned.

  As a commercial item of the surface treatment agent, for example, “KBM 22” (dimethyl dimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM 403” (3-glycidoxypropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Shin-Etsu Chemical Co., Ltd. "KBM 803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical "KBE 903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM 573" (N-phenyl-3-aminopropyltrimethoxy) Silane), Shin-Etsu Chemical "KBM5783" (N-phenyl-3-aminooctyl trimethoxysilane), Shin-Etsu Chemical "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical "KBM 103" (Phenyltrimethoxysilane), Shin-Etsu Chemical "KBM-4803" ( Chain epoxy type silane coupling agent), and the like. Among them, a nitrogen atom-containing silane coupling agent is preferable, an aminosilane-based coupling agent containing a phenyl group is more preferable, and N-phenyl-3-aminoalkyltrimethoxysilane is more preferable. Moreover, a surface treatment agent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

The extent of surface treatment with a surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (D) inorganic filler. Carbon content per unit surface area of the inorganic filler (D) is, (D) from the viewpoint of the dispersibility of the inorganic filler improved, preferably 0.02 mg / m ² or more, more preferably 0.1 mg / m ² or more, Particularly preferably, it is 0.2 mg / m ² or more. On the other hand, the amount of carbon is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, particularly preferably from the viewpoint of suppressing the melt viscosity of the resin composition and the increase in the melt viscosity in sheet form. Is less than 0.5 mg / m ² .

  The amount of carbon per unit surface area of the (D) inorganic filler is obtained by washing the surface-treated (D) inorganic filler with a solvent (for example, methyl ethyl ketone (hereinafter sometimes abbreviated as "MEK")). , Can measure. Specifically, a sufficient amount of methyl ethyl ketone and (D) inorganic filler surface-treated with a surface treatment agent are mixed, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. Then, after removing a supernatant liquid and making solid content dry, it can measure the amount of carbon per unit surface area of the (D) inorganic filler using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

  The amount of the (D) inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass, with respect to 100% by mass of non-volatile components in the resin composition. The content is 80% by mass or more, preferably 95% by mass or less, more preferably 93% by mass or less, and still more preferably 91% by mass or less. When the amount of the inorganic filler (D) is in the above range, the desired effect of the present invention can be significantly obtained, and in particular, the linear thermal expansion coefficient of the resin composition can be effectively lowered.

[6. (E) Hardening accelerator]
The resin composition may contain (E) a curing accelerator as an optional component. By using a curing accelerator, curing can be promoted when curing the resin composition.

  Examples of the curing accelerator (E) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

  As a phosphorus-based curing accelerator, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate Tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate and the like. Among them, triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene, 4-pyrrolidinopyridine etc. are mentioned. Among these, 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

  Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 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-one 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 isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H- Pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline 2-phenylimidazole compounds of imidazoline and the like and an imidazole compound and adduct of the epoxy resin. Among them, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

  A commercial item may be used as an imidazole series hardening accelerator, for example, "P200-H50" by Mitsubishi Chemical Co., Ltd .; "2E4MZ" by Shikoku Kasei Co., Ltd .; etc. are mentioned.

  As the guanidine-based curing accelerator, for example, dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine, diphenyl guanidine, trimethyl guanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1-( - tolyl) biguanide, and the like. Among them, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferable.

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

  When the resin composition contains (E) a curing accelerator, the amount of the (E) curing accelerator is preferably 100% by mass of the resin component of the resin composition from the viewpoint of obtaining the desired effect of the present invention. 0.01 mass%-3 mass% are preferable, 0.03 mass%-1.5 mass% are more preferable, 0.05 mass%-1 mass% are more preferable.

[7. (F) Optional Additives]
The resin composition may further contain optional additives as optional components in addition to the components described above. Such additives include, for example, organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; thermoplastic resins; thickeners; antifoaming agents; leveling agents; Resin additives such as flame retardants; One of these additives may be used alone, or two or more thereof may be used in combination in an arbitrary ratio.

  The above-mentioned resin composition may contain a solvent, if necessary, but is preferably a non-solvent resin composition substantially free of a solvent. Thus, even if it does not contain a solvent, the above-mentioned resin composition can be fluidized when it is molded using a compression molding method, and excellent compression moldability can be realized. Therefore, this resin composition can be used as a solvent-free resin composition. It becomes possible to suppress generation | occurrence | production of a flow mark by using as a non-solvent resin composition. The phrase "substantially free of solvent" means, for example, that the content of the solvent is 1% by mass or less based on the entire solventless resin composition.

[8. Method for producing resin composition]
The resin composition can be produced, for example, by a method of stirring the blended components using a stirring apparatus such as a rotary mixer.

[9. Properties of Resin Composition]
The resin composition described above is excellent in compression moldability. Therefore, when forming a resin composition layer on a circuit board or a semiconductor chip by a compression molding method, it is possible to fill the resin composition to every corner. Therefore, by curing the above-mentioned resin composition layer, it is possible to obtain an insulating layer excellent in insulation reliability and a sealing layer excellent in sealing reliability.

  For example, the resin composition described above is compression molded on a 12-inch silicon wafer using a compression mold apparatus (mold temperature: 130 ° C., mold pressure: 6 MPa, cure time: 10 minutes) to a thickness of 300 μm. A resin composition layer is formed. In this case, usually, the resin composition can be filled while suppressing the occurrence of flow marks.

  Moreover, according to the resin composition mentioned above, the layer of the hardened | cured material which can suppress curvature can be obtained. Therefore, by using this resin composition, it is possible to obtain the insulating layer and the sealing layer capable of suppressing the warpage of the circuit board and the semiconductor chip package. For example, using the resin composition described above, a cured product layer of the resin composition is formed on a 12-inch silicon wafer by the method described in the examples to produce a sample substrate. In this case, when the sample substrate is heated and cooled in the order of 35 ° C., 260 ° C. and 35 ° C., the amount of warpage measured by the method described in the examples can be usually less than 2 mm.

Moreover, according to the resin composition mentioned above, the hardened | cured material with a low linear thermal expansion coefficient can be obtained. Therefore, by using this resin composition, an insulating layer and a sealing layer having a low linear thermal expansion coefficient can be obtained.
For example, using the resin composition described above, a cured product for evaluation is manufactured by the method described in the examples, and the linear thermal expansion coefficient of the cured product for evaluation is measured. In this case, the linear thermal expansion coefficient to be obtained is usually 10 ppm / ° C. or less, preferably 9.5 ppm / ° C. or less, more preferably 9 ppm / ° C. or less. The lower limit is not particularly limited, and is usually 0 ppm / ° C., preferably 1 ppm / ° C. or more.

Moreover, the resin composition mentioned above can obtain the hardened | cured material with a high glass transition temperature (Tg) normally. Therefore, by using this resin composition, an insulating layer and a sealing layer having a high glass transition temperature can be obtained.
For example, using the resin composition described above, a cured product for evaluation is manufactured by the method described in the examples, and the glass transition temperature of the cured product for evaluation is measured. In this case, the obtained glass transition temperature is usually 130 ° C. or more, preferably 140 ° C. or more, more preferably 150 ° C. or more. The upper limit is not particularly limited, and is usually 300 ° C. or less, preferably 290 ° C. or less.

Moreover, the resin composition mentioned above exhibits the characteristic that the viscosity is usually low. Therefore, by using this resin composition, it becomes excellent in the handling property at the time of performing compression molding using a compression mold apparatus.
For example, using a RE80 viscometer (0.2 to 0.3 ml of the resin composition to be measured, measurement chamber temperature 25.0 ° C.), the rotational speed of the rotor is set to 1 rpm, and the viscosity after 120 seconds is measured. . In this case, the viscosity of the resin composition can be usually less than 500 Pa · s, preferably less than 400 Pa · s.

The inventors speculate as follows that the resin composition of the present invention can provide the above-mentioned excellent advantages. However, the technical scope of the present invention is not limited by the mechanism described below.
Since the resin composition described above contains a compound having a (C) rotaxane structure which is excellent in flexibility, the increase in viscosity is suppressed and the flowability at the time of compression molding is excellent. Therefore, since the resin composition can easily enter small gaps, excellent compression moldability is achieved.
Further, the (D) inorganic filler contained in the resin composition has a smaller degree of expansion and contraction due to temperature change, as compared with the resin component. Therefore, the linear thermal expansion coefficient of the cured product of the resin composition can be lowered.
Further, as described above, since the (D) inorganic filler has a small degree of expansion and contraction due to temperature change, even if temperature change occurs, stress caused by the temperature change can be reduced. Further, since the compound having the (C) rotaxane structure can function as a flexible flexible component, even if a stress occurs in the cured product, the compound having the (C) rotaxane structure can absorb the stress. Therefore, since generation | occurrence | production of the stress which may cause curvature can be suppressed, suppression of curvature is possible.

  The resin composition may be liquid or solid, but is preferably liquid at the time of molding. For example, a resin composition which is liquid at normal temperature (for example, 20 ° C.) may be molded by compression molding at ordinary temperature without special temperature adjustment, or may be heated by an appropriate temperature and molded by compression molding You may In addition, since a resin composition which is solid at normal temperature can usually be made liquid by adjusting the temperature to a higher temperature (for example, 130 ° C.), molding by a compression molding method is possible by appropriate temperature adjustment such as heating. It is possible. The above-mentioned resin composition can usually be liquid at an appropriate temperature without containing a solvent, and can be used, for example, as a liquid sealant.

[10. Applications of Resin Composition]
The sealing layer and the insulating layer can be formed by the cured product of the above-mentioned resin composition by utilizing the advantages described above. Therefore, this resin composition can be used as a resin composition for semiconductor sealing or for an insulating layer.

  For example, the resin composition is a resin composition (a resin composition for an insulating layer of a semiconductor chip package) for forming an insulating layer of a semiconductor chip package, and a circuit board (including a printed wiring board). It can be used suitably as a resin composition (resin composition for insulating layers of a circuit board) for forming an insulating layer.

  In addition, for example, the resin composition described above can be suitably used as a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip).

  Examples of semiconductor chip packages to which the sealing layer or the insulating layer formed of the cured product of the above resin composition can be applied include FC-CSP, MIS-BGA package, ETS-BGA package, Fan-out type WLP (Wafer) Examples include Level Package, Fan-in type WLP, Fan-out type PLP (Panel Level Package), and Fan-in type PLP.

  Moreover, the above-mentioned resin composition may be used as an underfill material, and may be used as a material of MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate, for example.

  Furthermore, the resin composition described above can be used in a wide range of applications in which the resin composition is used, such as resin sheets, sheet-like laminate materials such as prepregs, solder resists, die bonding materials, hole filling resins, component embedding resins and the like.

[11. Resin sheet]
The resin sheet of the present invention has a support and a resin composition layer provided on the support. The resin composition layer is a layer containing the resin composition of the present invention, and is usually formed of a resin composition.

  The thickness of the resin composition layer is preferably 600 μm or less, more preferably 550 μm or less, still more preferably 500 μm or less, 400 μm or less, 350 μm or less, 300 μm or less, or 200 μm or less from the viewpoint of thinning. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be, for example, 1 μm or more, 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 abbreviated as "PEN"). Polycarbonates (hereinafter sometimes abbreviated as "PC"); Acrylic polymers such as polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA"); Cyclic polyolefins; Triacetylcellulose (below) They may be abbreviated as "TAC"); polyether sulfide (hereinafter sometimes abbreviated as "PES"); polyether ketone; polyimide; and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, copper foil, aluminum foil, etc. are mentioned as metal foil, for example. Among them, copper foil is 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 another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) You may use.

  The surface of the support to be bonded to the resin composition layer may be subjected to treatments such as mat treatment, corona treatment, antistatic treatment and the like.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. As the release agent used for the release layer of the support with release layer, for example, one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin can be mentioned. . As a commercial item of a mold release agent, "SK-1", "AL-5", "AL-7" etc. which are alkyd resin type mold release agents and are made by Lintec Corporation are mentioned, for example. Further, examples of the release layer-provided support include “Lumirror T60” manufactured by Toray Industries, Inc .; “Purex” manufactured by Teijin Limited; “UniPeel” manufactured by Unitika; and the like.

  The thickness of the support is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using the support body with a release layer, it is preferable that the thickness of the support body with a release layer is the said range.

  The resin sheet can be produced, for example, by applying the resin composition onto a support using a coating apparatus such as a die coater. In addition, if necessary, the resin composition may be dissolved in an organic solvent to prepare a resin varnish, and the resin varnish may be applied to manufacture a resin sheet. By using a solvent, the viscosity can be adjusted to improve the coatability. When a resin varnish is used, the resin varnish is generally dried after application to form a resin composition layer.

  Organic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitol such as cellosolve and butyl carbitol Solvents; Aromatic hydrocarbon solvents such as toluene and xylene; Amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; and the like. The organic solvents may be used alone or in combination of two or more at any ratio.

  Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it changes also with the boiling points of the organic solvent in a resin varnish, when using the resin varnish containing 30 mass%-60 mass% organic solvent, for example, resin composition by making it dry at 50 degreeC-150 degreeC for 3 minutes-10 minutes Object layer can be formed.

  The resin sheet may optionally contain any layer other than the support and the resin composition layer. For example, in the resin sheet, a protective film conforming to the support may be provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent adhesion of dust and the like to the surface of the resin composition layer and scratches. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. Also, the resin sheet can be wound and stored in a roll shape.

  The resin sheet can be suitably used for forming an insulating layer in the manufacture of a semiconductor chip package (resin sheet for insulation of semiconductor chip package). For example, a resin sheet can be used for forming an insulating layer of a circuit board (resin sheet for insulating layer of circuit board). Examples of packages using such a substrate include FC-CSP, MIS-BGA package, and ETS-BGA package.

  Further, the resin sheet can be suitably used for sealing a semiconductor chip (resin sheet for sealing a semiconductor chip). Examples of applicable semiconductor chip packages include Fan-out WLP, Fan-in WLP, Fan-out PLP, and Fan-in PLP.

  Alternatively, the resin sheet may be used as a material of MUF used after the semiconductor chip is connected to the substrate.

  Furthermore, the resin sheet can be used in a wide variety of other applications where high insulation reliability is required. For example, the resin sheet can be suitably used to form an insulating layer of a circuit board such as a printed wiring board.

[12. Circuit board]
The circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention. The circuit board can be manufactured, for example, by a manufacturing method including the following steps (1) and (2).
(1) A step of forming a resin composition layer on a substrate.
(2) A step of thermally curing the resin composition layer to form an insulating layer.

  At a process (1), a base material is prepared. Examples of the substrate include substrates such as glass epoxy substrates, metal substrates (stainless steel and cold rolled steel plate (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting type polyphenylene ether substrates and the like. Moreover, the base material may have a metal layer such as copper foil on the surface as a part of the base material. For example, a substrate having a peelable first metal layer and a second metal layer on both surfaces may be used. When such a base material is used, a conductor layer as a wiring layer which can function as a circuit wiring is usually formed on the surface of the second metal layer opposite to the first metal layer. As a base material which has such a metal layer, the ultra-thin copper foil "Micro Thin" with a carrier copper foil by Mitsui Metal Mining Co., Ltd. is mentioned, for example.

  In addition, a conductor layer may be formed on one or both surfaces of the substrate. In the following description, a member including a base and a conductor layer formed on the surface of the base may be referred to as “base with wiring layer” as appropriate. The conductor material contained in the conductor layer is, for example, one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Materials containing the above metals can be mentioned. As a conductor material, a single metal may be used, or an alloy may be used. Examples of the alloy include alloys of two or more metals selected from the above group (eg, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as a single metal, and the nickel-chromium alloy as an alloy, from the viewpoint of versatility of conductor layer formation, cost, and ease of patterning. , Copper-nickel alloy, copper-titanium alloy; Among them, a single metal of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and a nickel-chromium alloy are more preferable, and a single metal of copper is particularly preferable.

  The conductor layer may be patterned, for example, to function as a wiring layer. At this time, the line (circuit width) / space (width between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10 μm or less It is preferably 5/5 μm or less, more preferably 1/1 μm or less, particularly preferably 0.5 / 0.5 μm or more. The pitch does not have to be the same throughout the conductor layer. The minimum pitch of the conductor layers may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

  The thickness of the conductor layer depends on the design of the circuit board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 μm to 20 μm, and particularly preferably 15 μm to 20 μm.

  The conductive layer is formed, for example, by a process of laminating a dry film (photosensitive resist film) on a substrate, exposing and developing the dry film under predetermined conditions using a photomask to form a pattern to form a pattern dry. It can be formed by a method including a step of obtaining a film, a step of forming a conductor layer by a plating method such as electrolytic plating using the developed pattern dry film as a plating mask, and a step of peeling the pattern dry film. As a dry film, the photosensitive dry film which consists of a photoresist composition can be used, for example, the dry film formed with resin, such as novolak resin and an acrylic resin, can be used. The lamination conditions of the base material and the dry film may be the same as the lamination conditions of the base material and the resin sheet described later. Peeling of the dry film can be carried out using, for example, an alkaline peeling solution such as sodium hydroxide solution.

  After preparing the substrate, the resin composition layer is formed on the substrate. When the conductor layer is formed on the surface of the substrate, the resin composition layer is preferably formed such that the conductor layer is embedded in the resin composition layer.

  Formation of a resin composition layer is performed by laminating | stacking a resin sheet and a base material, for example. This lamination can be performed, for example, by bonding the resin composition layer to the substrate by heat-pressing the resin sheet onto the substrate from the support side. Examples of the member (hereinafter, also referred to as "heat-pressing member") for heat-pressing the resin sheet to the base material include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll, etc.). Be In addition, it is preferable to press via elastic materials, such as heat resistant rubber, so that a resin sheet may fully follow surface unevenness of a substrate instead of pressing a thermocompression bonding member directly to a resin sheet.

  The lamination of the substrate and the resin sheet may be performed, for example, by vacuum lamination. In the vacuum laminating method, the heating and pressing temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C. The heat pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure conditions of a pressure of 13 hPa or less.

  After lamination, the laminated resin sheet may be subjected to a smoothing treatment by normal pressure (atmospheric pressure), for example, by pressing the heat pressure-bonding member from the support side. The pressing conditions for the smoothing treatment can be the same as the heating and pressing conditions for the above-mentioned lamination. In addition, you may perform lamination | stacking and smoothing processing continuously using a vacuum laminator.

  Moreover, formation of a resin composition layer can be performed by the compression molding method, for example. The molding conditions may be the same as the method for forming the resin composition layer in the step of forming the sealing layer of the semiconductor chip package described later.

  After the resin composition layer is formed on the substrate, the resin composition layer is thermally cured to form an insulating layer. The heat curing conditions of the resin composition layer vary depending on the type of the resin composition, but the curing temperature is usually in the range of 120 ° C. to 240 ° C. (preferably 150 ° C. to 220 ° C., more preferably 170 ° C. to 200 ° C. Range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

  Before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheating treatment in which the temperature is lower than the curing temperature. For example, prior to heat curing of the resin composition layer, the resin composition layer is usually at a temperature of 50 ° C. or more and less than 120 ° C. (preferably 60 ° C. or more and 110 ° C. or less, more preferably 70 ° C. or more and 100 ° C. or less). May be preheated usually for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

As described above, a circuit board having an insulating layer can be manufactured. In addition, the method of manufacturing a circuit board may further include an optional step.
For example, when a circuit board is manufactured using a resin sheet, the method for manufacturing a circuit board may include the step of peeling the support of the resin sheet. The support may be peeled off before heat curing of the resin composition layer, or may be peeled off after heat curing of the resin composition layer.

  The method of manufacturing the circuit board may include, for example, a step of polishing the surface of the insulating layer after forming the insulating layer. The polishing method is not particularly limited. For example, a surface grinder can be used to polish the surface of the insulating layer.

  The method of manufacturing a circuit board may include, for example, a step (3) of connecting conductor layers to each other, a step of forming a hole in a so-called insulating layer. Thus, holes such as via holes and through holes can be formed in the insulating layer. Examples of the method for forming the via holes include laser irradiation, etching, mechanical drilling, and the like. The dimensions and shape of the via holes may be determined appropriately according to the design of the circuit board. In the step (3), interlayer connection may be performed by polishing or grinding of the insulating layer.

  After the formation of the via holes, it is preferable to carry out the step of removing the smear in the via holes. This process is sometimes called a desmear process. For example, in the case where the formation of the conductor layer on the insulating layer is performed by a plating step, wet desmear treatment may be performed on the via hole. In the case where the formation of the conductor layer on the insulating layer is performed by a sputtering process, a dry desmear process such as a plasma treatment process may be performed. Furthermore, the insulating layer may be roughened by a desmear process.

  Alternatively, the insulating layer may be roughened before the conductor layer is formed over the insulating layer. According to this roughening treatment, the surface of the insulating layer including the inside of the via hole is usually roughened. As roughening treatment, either dry or wet roughening treatment may be performed. Plasma treatment etc. are mentioned as an example of dry roughening treatment. Further, as an example of the wet roughening treatment, there may be mentioned a method of performing swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution in this order.

  After forming the via holes, a conductor layer is formed on the insulating layer. By forming the conductor layer at the position where the via hole is formed, the newly formed conductor layer and the conductor layer on the surface of the base are electrically connected, and interlayer connection is performed. Examples of the method for forming the conductor layer include a plating method, a sputtering method, a vapor deposition method and the like, and among these, the plating method is preferable. In a preferred embodiment, the surface of the insulating layer is plated by a suitable method such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. When the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a subtractive method. The material of the conductor layer to be formed may be a single metal or an alloy. The conductor layer may have a single-layer structure, or may have a multilayer structure including two or more layers of different types of materials.

  Here, an example of an embodiment in which a conductor layer is formed on an insulating layer will be described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed plating seed layer, a mask pattern is formed to expose a part of the plating seed layer, corresponding to the desired wiring pattern. After an electrolytic plating layer is formed by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by a process such as etching to form a conductor layer having a desired wiring pattern. In addition, when forming a conductor layer, the dry film used for formation of a mask pattern is the same as that of the said dry film.

  The method for producing a circuit board may include the step (4) of removing the substrate. By removing the substrate, a circuit board having an insulating layer and a conductor layer embedded in the insulating layer can be obtained. This step (4) can be performed, for example, when using a substrate having a peelable metal layer.

[13. Semiconductor chip package]
A semiconductor chip package according to a first embodiment of the present invention includes the circuit board described above and a semiconductor chip mounted on the circuit board. The semiconductor chip package can be manufactured by bonding a semiconductor chip to a circuit substrate.

  The bonding condition between the circuit board and the semiconductor chip can be any condition that allows the terminal electrode of the semiconductor chip and the circuit wiring of the circuit board to be conductively connected. For example, conditions used in flip chip mounting of semiconductor chips can be employed. Also, for example, bonding may be performed between the semiconductor chip and the circuit substrate via an insulating adhesive.

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

  Further, as another example of the bonding method, there is a method of reflowing and bonding a semiconductor chip to a circuit board. The reflow conditions may be in the range of 120 ° C. to 300 ° C.

  After bonding the semiconductor chip to the circuit substrate, the semiconductor chip may be filled with a mold underfill material. As the mold underfill material, the above-described resin composition may be used, or the above-described resin sheet may be used.

  The semiconductor chip package which concerns on 2nd embodiment of this invention contains a semiconductor chip and the hardened | cured material of the said resin composition which seals this semiconductor chip. In such a semiconductor chip package, the cured product of the resin composition usually functions as a sealing layer. As a semiconductor chip package concerning a second embodiment, Fan-out type WLP is mentioned, for example.

A method of manufacturing such a semiconductor chip package is
(A) 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) peeling the base material and the temporary fixing film from the semiconductor chip,
(E) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled;
(F) forming a rewiring layer as a conductor layer on the rewiring formation layer;
(G) forming a solder resist layer on the rewiring layer;
including. Further, the method of manufacturing the semiconductor chip package is
(H) A step of dicing and singulating a plurality of semiconductor chip packages into individual semiconductor chip packages may be included.

(Step (A))
A process (A) is a process of laminating a temporary fixed film on a substrate. The lamination conditions of the substrate and the temporary fixing film may be the same as the lamination conditions of the substrate and the resin sheet in the method of manufacturing a circuit board.

  As the base material, for example, silicon wafer; glass wafer; glass substrate; metal substrate such as copper, titanium, stainless steel, cold rolled steel plate (SPCC) or the like; FR-4 substrate, etc. Thermally cured substrates; substrates made of bismaleimide triazine resin such as BT resin; and the like.

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

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

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

  It is preferable to perform the formation of the resin composition layer by the compression molding method by utilizing the excellent compression moldability of the resin composition. In the compression molding method, usually, a semiconductor chip and a resin composition are placed in a mold, and pressure and optionally heat are applied to the resin composition in the mold to form a resin composition layer covering the semiconductor chip.

  The specific operation of the compression molding method may be, for example, as follows. The upper and lower molds are prepared as compression molding molds. Moreover, a resin composition is apply | coated to the semiconductor chip temporarily fixed on the temporarily fixed film as mentioned above. The semiconductor chip coated with the 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, heat and pressure are applied to the resin composition, and compression molding is performed.

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

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

  The formation of the resin composition layer may be performed by laminating a resin sheet 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 resin sheet and the semiconductor chip. The lamination of the resin sheet and the semiconductor chip can be generally performed using the semiconductor chip instead of the base material in the same manner as the lamination of the resin sheet and the base material in the method of manufacturing a circuit board.

  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. Thus, the semiconductor chip is sealed with the cured product of the resin composition. The heat curing conditions for the resin composition layer may be the same as the heat curing conditions for the resin composition layer in the method for producing a circuit board. Furthermore, before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheating treatment in which the temperature is lower than the curing temperature. The processing conditions of this preheating processing may adopt the same conditions as the preheating processing in the method of manufacturing a circuit board.

(Step (D))
A process (D) is a process of peeling a base material and a temporarily fixed film from a semiconductor chip. As the peeling method, it is desirable to adopt an appropriate method according to the material of the temporary fixing film. As a peeling method, for example, a method of heating, foaming or expanding a temporarily fixed film and peeling is mentioned. Moreover, as a peeling method, an ultraviolet-ray is irradiated to a temporary fixing film through a base material, for example, The method of reducing the adhesive force of a temporary fixing film and peeling is mentioned.

In the method of heating, foaming or expanding and peeling the temporarily fixed film, the heating conditions are usually 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. Further, in the method for peeling by reducing the adhesive strength of the temporary fixing film by ultraviolet irradiation, irradiation amount of ultraviolet rays is ^{usually, 10mJ / cm 2 ~1000mJ / cm} 2.

(Step (E))
A process (E) is a process of forming the rewiring formation layer as an insulating layer in the surface which peeled the base material and temporary fixing film of a semiconductor chip.

  The material of the redistribution layer can be any material having insulation. Among them, photosensitive resins and thermosetting resins are preferable from the viewpoint of easiness of production of semiconductor chip packages. Moreover, you may use the resin composition of this invention as this thermosetting resin.

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

  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 light the rewiring layer of the irradiated portion. Cure. As an active energy ray, an ultraviolet-ray, a visible ray, an electron beam, an X ray etc. are mentioned, for example, Especially an ultraviolet-ray is preferable. The irradiation amount and irradiation time of the ultraviolet light can be appropriately set according to the photosensitive resin. As an exposure method, for example, a contact exposure method in which a mask pattern is brought into intimate contact with a rewiring formation layer and exposure, a non-contact exposure method in which a mask pattern is exposed using parallel rays without coming in contact with a rewiring formation layer Can be mentioned.

  After the rewiring layer is photocured, the rewiring layer is developed to remove the unexposed area to form a via hole. The development may be either wet development or dry development. Examples of the development method include a dip method, a paddle method, a spray method, a brushing method, and a scraping method. From the viewpoint of resolution, the paddle method is preferable.

  Examples of the method for forming the via hole when the material of the rewiring formation layer is a thermosetting resin include laser irradiation, etching, mechanical drilling and the like. Among them, laser irradiation is preferred. The laser irradiation can be performed using a suitable laser processing machine using a light source such as a carbon dioxide gas laser, a UV-YAG laser, or an excimer laser.

  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, 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 formation layer.

(Step (F))
The step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring formation layer. The method of forming the rewiring layer on the rewiring formation layer may be the same as the method of forming the conductor layer on the insulating layer in the method of manufacturing the circuit board. Further, the step (E) and the step (F) may be repeated to alternately build up the rewiring layer and the rewiring formation layer (build up).

(Step (G))
The step (G) is a step of forming a solder resist layer on the redistribution layer. As a material of the solder resist layer, any material having an insulating property can be used. Among them, photosensitive resins and thermosetting resins are preferable from the viewpoint of easiness of production of semiconductor chip packages. Moreover, you may use the resin composition of this invention as a thermosetting resin.

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

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

  The semiconductor chip package according to the third embodiment of the present invention is, for example, a cured product of the resin composition of the present invention in the rewiring formation layer 130 or the solder resist layer 150 in the semiconductor chip package 100 whose example is shown in FIG. A semiconductor chip package formed by

[14. Semiconductor device]
Examples of semiconductor devices on which the semiconductor chip package described above is mounted include electric products (for example, computers, mobile phones, smart phones, tablet devices, wearable devices, digital cameras, medical devices, televisions, etc.) and vehicles (for example, And various semiconductor devices provided for motorcycles, automobiles, trains, ships, aircrafts, etc.).

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass" unless otherwise specified. Moreover, the operation described below was performed in an environment of normal temperature and normal pressure unless otherwise specified.

[Used (D) ingredient]
Inorganic filler A: "ST7030-20" (manufactured by Nippon Steel & Sumikin Materials Co., Ltd., average particle diameter: 6.2 μm) is treated with "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) The resultant was used as an inorganic filler A.

Example 1
2 parts of alicyclic epoxy resin (made by Daicel, "CEL2021P", epoxy equivalent 136 g / eq.), 110 parts of inorganic filler A, polyrotaxane fine particles (made by Advanced Soft Materials, "SH2400B-007", axial molecule Contains a polyethylene glycol chain, and the cyclic molecule contains cyclodextrins) 0.6 part, an acid anhydride curing agent (manufactured by New Japan Chemical Co., Ltd., “MH-700”, acid anhydride equivalent 164 g / eq.) 10 Parts, 3 parts of naphthalene ether type epoxy resin (manufactured by DIC, "HP6000L", epoxy equivalent 213 g / eq.), 7 parts of glycidyl amine type epoxy resin (manufactured by ADEKA, "EP3950S", epoxy equivalent 95 g / eq.) Mix 0.1 parts of a curing accelerator (Shikoku Kasei Co., Ltd., “1B2PZ”), and uniformly disperse with a mixer The resin composition was prepared.

Example 2
In Example 1, 0.6 part of polyrotaxane fine particles (Advanced Soft Materials, Inc., “SH2400B-007”) and polyrotaxane (Advanced Soft Materials, Inc., “SH1310P” in methyl ethyl ketone 40% solution, shaft molecule is It contains a polyethylene glycol chain, and the cyclic molecule contains cyclodextrins. A resin composition was produced in the same manner as Example 1 except for the above matters.

[Example 3]
In Example 1, 2 parts of an alicyclic epoxy resin (made by Daicel, "CEL 2021 P", epoxy equivalent 136 g / eq.), A bisphenol type epoxy resin (made by Nippon Steel Sumikin Chemical Co., Ltd., "ZX1059", bisphenol A type and bisphenol The mixture was changed to 2 parts of a 1: 1 mixture of Form F, epoxy equivalent weight 169 g / eq.). A resin composition was produced in the same manner as Example 1 except for the above matters.

Example 4
3 parts of alicyclic epoxy resin (made by Daicel, "CEL2021P", epoxy equivalent 136 g / eq.), 110 parts of inorganic filler A, 1 part of polyrotaxane fine particles (manufactured by Advanced Soft Materials, "SH2400B-007") , Triazine-containing phenol novolak resin (manufactured by DIC, "LA-7054", hydroxyl group equivalent 125 g / eq., Nitrogen content about 12% by weight, solid content 60% by weight MEK solution) 8.3 parts, naphthalene ether type 4 parts of epoxy resin ("HP6000L" manufactured by DIC, epoxy equivalent 213 g / eq.), 8 parts of glycidyl amine type epoxy resin (manufactured by ADEKA, "EP3950S", epoxy equivalent 95 g / eq.), Curing accelerator (Shikoku Chemicals Made by mixing 0.1 parts of “1B2PZ”) and uniformly dispersed by a mixer A product was made.

[Example 5]
In Example 4, 8.3 parts of a triazine-containing phenol novolak resin (“LA-7054” manufactured by DIC, a hydroxyl equivalent of 125 g / eq., A nitrogen content of about 12% by weight, and a solid content of 60% by weight) It was changed to 5 parts of liquid novolak-type phenol curing agent (manufactured by Meito Kasei Co., Ltd., "MEH-8000H", phenolic hydroxyl group equivalent weight 141 g / eq.). A resin composition was produced in the same manner as in Example 4 except for the matters described above.

Comparative Example 1
In Example 1, 0.6 parts of polyrotaxane fine particles (manufactured by Advanced Soft Materials Co., Ltd., “SH2400B-007”) was changed to 0.6 parts of rubber particles (manufactured by Ganz Chemical Co., Ltd., Staphyloid AC3816N). A resin composition was produced in the same manner as Example 1 except for the above matters.

Comparative Example 2
In Example 1, 0.6 part of polyrotaxane fine particles (manufactured by Advanced Soft Materials, “SH2400B-007”) and polybutadiene epoxy resin (manufactured by Nippon Soda Co., Ltd., “JP200”, epoxy equivalent weight: 210 to 2406 g / eq.) It changed to 2 copies. A resin composition was produced in the same manner as Example 1 except for the above matters.

[Measurement of viscosity]
0.2 to 0.3 ml of the resin composition to be measured was weighed out with a syringe in a measuring chamber of RE 80 type viscometer (manufactured by Toki Sangyo Co., Ltd.). At the time of measurement, the temperature of the measurement chamber of the viscometer was controlled to 25.0 ° C. by an external circulation type thermostat. The rotational speed of the rotor was set to 1 rpm, and the viscosity after 120 seconds was measured (unit: Pa · s). If the viscosity is 500 Pa · s or more, handling becomes difficult when performing compression molding, so “×” is used, and those with a viscosity of 400 Pa · s or more and less than 500 Pa · s are “Δ”, and the viscosity is 400 Pa · s. Less than one is "○".

[Evaluation of flow mark]
The resin compositions produced in the examples and comparative examples were compression molded on a 12-inch silicon wafer using a compression mold apparatus (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes). A 300 μm thick resin composition layer was formed. Thereafter, after heating at 150 ° C. for 60 minutes, the flow mark was visually confirmed on the surface of the resin composition layer. Those with flow marks on the entire wafer are marked with “x”, those with flow marks present only at the wafer edge are marked with “Δ”, and those without flow marks are marked with “o”.

[Measurement of warpage]
The resin compositions produced in the examples and comparative examples were compression molded on a 12-inch silicon wafer using a compression mold apparatus (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes). A 300 μm thick resin composition layer was formed. Thereafter, the resin composition layer was thermally cured by heating at 150 ° C. for 60 minutes. Thus, a sample substrate including the silicon wafer and the cured product layer of the resin composition layer was obtained.

  The amount of warpage when the sample substrate was heated and cooled in the order of 35 ° C., 260 ° C. and 35 ° C. was measured using a shadow moiré measurement apparatus (manufactured by Akorometrix, “Thermoire AXP”). The measurement was performed in accordance with JEITA EDX-7311-24 standard of the Institute of Electronics, Information and Communication Technology. Specifically, with the virtual plane calculated by the least squares method of all data of the sample substrate surface in the measurement area as a reference plane, the difference between the minimum value and the maximum value in the vertical direction from the reference plane was determined as the amount of warpage. The amount of warpage was less than 2 mm as "o", and the amount of warpage was 2 mm or more as "x".

[Measurement of linear thermal expansion coefficient (CTE) and glass transition temperature (Tg)]
The resin compositions produced in the examples and comparative examples were compression molded on a 12-inch SUS wafer using a compression mold apparatus (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes). A 300 μm thick resin composition layer was formed. Thereafter, after heating at 150 ° C. for 60 minutes, the resin composition layer was peeled off from the SUS wafer to obtain a cured product. The cured product was cut into a test piece having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a tensile load method using a Rigaku thermomechanical analyzer (Thermo Plus TMA 8310).

  After the test piece was attached to the apparatus, measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature rising rate of 5 ° C./min. The average linear thermal expansion coefficient at 25 ° C. to 150 ° C. in the second measurement was determined. The glass transition temperature was calculated from the point at which the slope of the dimensional change signal in the second measurement changes. The case where the glass transition temperature is 130 ° C. or more is “o”, and the case less than 130 ° C. is “x”. Moreover, what the crack generate | occur | produced in the test piece during measurement of glass transition temperature was described as "crack."

The component used for preparation of Examples 1-5 and Comparative Examples 1-2, and the compounding quantity (non-volatile-content conversion) were shown in the following table. Abbreviations etc. in the following table are as follows.
CEL 2021 P: alicyclic epoxy resin (manufactured by Daicel, epoxy equivalent 136 g / eq.)
ZX1059: Bisphenol type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169 g / eq.)
HP6000L: Naphthylene ether type epoxy resin (manufactured by DIC, epoxy equivalent 213 g / eq.)
EP3950S: glycidyl amine type epoxy resin (manufactured by ADEKA, epoxy equivalent 95 g / eq.)
JP 200: polybutadiene epoxy resin (manufactured by Nippon Soda Co., Ltd., epoxy equivalent 210 to 2406 g / eq.)
MH-700: acid anhydride curing agent (manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent 164 g / eq.)
LA-7054: Triazine-containing phenol novolak resin (manufactured by DIC, hydroxyl equivalent 125 g / eq., NEK content about 12% by weight, solid content 60% by weight MEK solution)
MEH-8000H: liquid novolac type phenol curing agent (manufactured by Meiwa Kasei Co., Ltd., phenolic hydroxyl equivalent weight 141 g / eq.)
SH2400B-007: Polyrotaxane fine particles (manufactured by Advanced Soft Materials)
SH1310P: Polyrotaxane (manufactured by Advanced Soft Materials)
Inorganic filler A: "ST7030-20" (manufactured by Nippon Steel & Sumikin Materials Co., Ltd., average particle diameter: 6.2 μm) is treated with "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) Cured product 1B2PZ: Hardening accelerator (Shikoku Kasei Co., Ltd.)
AC3816N: rubber particles (Ganz Chemical Co., Ltd., Staphyloid AC3816N)

  Even in the case where the component (E) is not contained, it is confirmed that the result is similar to that of the above-mentioned example although there is a difference in degree.

Claims (16)

  A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) a compound having a rotaxane structure, and (D) an inorganic filler.   The resin composition according to claim 1, wherein the component (C) is a polyrotaxane.   The resin composition of Claim 1 or 2 whose content of (C) component is 0.1 mass% or more and 10 mass% or less, when the non volatile component of a resin composition is made into 100 mass%.   The resin composition according to any one of claims 1 to 3, wherein the component (C) is particulate.   The resin composition according to any one of claims 1 to 4, wherein the average particle diameter of the component (C) is 100 nm or more and 20000 nm or less.   The resin composition according to any one of claims 1 to 5, wherein the component (C) contains a cyclic molecule containing cyclodextrins.   The resin composition according to any one of claims 1 to 6, wherein the component (C) comprises an axial molecule containing a polyethylene glycol chain.   The resin composition according to any one of claims 1 to 7, wherein the weight average molecular weight of the axial molecule in the component (C) is 3,000 or more and 100,000 or less.   The inclusion amount of the cyclic molecule in the component (C) is 10% or more and 90% or less, assuming that the amount of cyclic molecule included in one axial molecule to a maximum extent is 100%. The resin composition according to any one of the preceding items.   The resin composition according to any one of claims 1 to 9, wherein the content of the component (D) is 50% by mass or more when the nonvolatile component of the resin composition is 100% by mass.   The resin composition according to any one of claims 1 to 10, wherein the component (B) contains any of a phenolic curing agent and an acid anhydride curing agent.   The resin composition according to any one of claims 1 to 11, which is a resin composition for encapsulating a semiconductor or for an insulating layer.   The resin composition according to any one of claims 1 to 12, which is a liquid resin composition.   The circuit board containing the insulating layer formed of the hardened | cured material of the resin composition of any one of Claims 1-13.   A semiconductor chip package comprising the circuit board according to claim 14 and a semiconductor chip mounted on the circuit board.   The semiconductor chip package containing the semiconductor chip and the hardened | cured material of the resin composition of any one of Claims 1-13 which seals the said semiconductor chip.

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