Resin composition

Abstract

The present invention provides a resin composition that can obtain a cured product with excellent warpage and brittleness suppression. The present invention is a resin composition comprising (A) an epoxy resin and (B) a curing agent, wherein the oxygen transmission coefficient of a cured product obtained by heat curing the resin composition at 180°C for 90 minutes is 3 cc / (atm·m 2 ·day·mm) or less, and the linear thermal expansion coefficient of the cured product is 4 to 15 ppm / °C.

Description

[0001] This application is a divisional application of Chinese patent application No. 201910815518.3, filed on August 30, 2019, entitled "Resin Composition". Technical Field

[0002] The present invention relates to: a resin composition comprising an epoxy resin and a curing agent; a resin ink comprising the above-mentioned resin composition; a resin ink layer formed from the above-mentioned resin ink; a resin sheet having a resin composition layer comprising the above-mentioned resin composition; and a semiconductor chip package comprising a cured product of the above-mentioned resin composition. Background Technology

[0003] In recent years, the demand for small, high-performance electronic devices such as smartphones and tablets has increased, leading to a growing demand for more functional insulating materials used in semiconductor packaging for these devices. Regarding such insulating layers, insulating layers formed by curing resin compositions are known (see, for example, Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent document 1: Japanese Patent Application Publication No. 2017-008312. Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] For insulating materials used in semiconductor chip packaging, it is required that they are not easily adversely affected even when subjected to high-temperature treatment to improve reliability. However, with the increasing demands for miniaturization and thin-film technology, most existing insulating materials still have room for improvement. In particular, due to the requirements of miniaturization and thin-film technology, the requirements for warpage suppression in packages have become more stringent in order to improve the stability and yield of micro-wiring formation or chip mounting. However, if the flexibility of the cured material is increased to improve warpage suppression, the mechanical properties will deteriorate during high-temperature treatment, making the cured material brittle. Therefore, it is known that it is difficult to simultaneously achieve warpage suppression and embrittlement suppression.

[0009] The objective of this invention is to provide a resin composition that yields a cured product with excellent warpage and embrittlement suppression.

[0010] Methods for solving problems

[0011] In order to achieve the objectives of this invention, the inventors conducted in-depth research and found that by adjusting the permeability coefficient and linear thermal expansion coefficient of the cured resin composition to a predetermined range, a cured product with excellent warpage suppression and embrittlement suppression can be obtained, thereby completing this invention.

[0012] That is, this invention includes the following:

[0013] [1] A resin composition comprising (A) an epoxy resin and (B) a curing agent, wherein the oxygen permeability coefficient of the cured product obtained by heat curing the resin composition at 180°C for 90 minutes is 3 cc / (atm·m). 2 For products with a linear thermal expansion coefficient of 4 to 15 ppm / ℃ (day·mm) or less, the above-mentioned cured products have a linear thermal expansion coefficient of 4 to 15 ppm / ℃.

[0014] [2] The resin composition according to [1] further comprises (C) an inorganic filler material;

[0015] [3] According to the resin composition of [2], when the non-volatile component in the resin composition is set to 100% by mass, the content of component (C) is 83% by mass or more;

[0016] [4] The resin composition according to [2] or [3], wherein the average particle size of component (C) is 2.5 μm or more;

[0017] [5] The resin composition according to any one of [1] to [4], wherein component (A) comprises a solid epoxy resin;

[0018] [6] The resin composition according to any one of [1] to [5], wherein component (A) comprises liquid epoxy resin, and when the resin component in the resin composition is set to 100% by mass, the content of liquid epoxy resin is 70% by mass or less;

[0019] [7] The resin composition according to any one of [1] to [6], wherein the epoxy equivalent of the epoxy resin included as component (A) is 400 g / eq. or less;

[0020] [8] The resin composition according to any one of [1] to [7], wherein component (B) comprises a phenolic curing agent or an anhydride curing agent;

[0021] [9] The resin composition according to any one of [1] to [8], wherein it further comprises (D) an elastomer;

[0022]

[10] According to the resin composition of [9], when the resin component in the resin composition is set to 100% by mass, the content of component (D) is 30% by mass or less;

[0023]

[11] The resin composition according to any one of [1] to

[10] , wherein the elongation at 23°C of the cured product obtained by heat curing the resin composition at 180°C for 24 hours is 0.7 or more, as measured according to JIS K7127, relative to the elongation at 23°C of the cured product obtained by heat curing the resin composition at 180°C for 90 minutes.

[0024]

[12] The resin composition according to any one of [1] to

[11] , wherein the resin composition is used to seal a semiconductor chip packaged with a semiconductor chip;

[0025]

[13] A resin ink comprising any one of the resin compositions described in [1] to

[11] ;

[0026]

[14] A resin ink layer formed of the resin ink described in

[13] and having a thickness of 100 μm or more;

[0027]

[15] A resin sheet comprising: a support body and a resin composition layer comprising any one of [1] to

[11] disposed on the support body;

[0028]

[16] The resin sheet according to

[15] , wherein the thickness of the above-mentioned resin composition layer is 100 μm or more;

[0029]

[17] A semiconductor chip package, wherein the cured product comprises the resin composition described in any one of [1] to

[11] .

[0030] The effects of the invention

[0031] According to the present invention, the following can be provided: a resin composition capable of producing a cured product with excellent warpage and embrittlement suppression; a resin ink comprising the above-mentioned resin composition; a resin ink layer formed from the above-mentioned resin ink; a resin sheet having a resin composition layer comprising the above-mentioned resin composition; and a semiconductor chip package comprising the cured product of the above-mentioned resin composition. Detailed Implementation

[0032] The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications without departing from the scope of the claims and their equivalents.

[0033] <Resin Composition>

[0034] The resin composition of the present invention comprises (A) an epoxy resin and (B) a curing agent. The cured product obtained by heat curing the resin composition of the present invention at 180°C for 90 minutes has a transmittance of 3 cc / (atm·m).2 The temperature range is below 1000°C (day / mm), and the linear thermal expansion coefficient of the cured material is 4–15 ppm / °C.

[0035] By using this resin composition, the desired effect of the present invention, which is to obtain a cured product with excellent warpage and embrittlement suppression, can be achieved.

[0036] In addition to (A) epoxy resin and (B) curing agent, the resin composition of the present invention may further contain any other components. Examples of such other components include: (C) inorganic filler, (D) elastomer, (E) rubber particles, (F) curing accelerator, (G) organic solvent, and (H) other additives. The components contained in the resin composition are described in detail below.

[0037] <(A) Epoxy Resin>

[0038] The resin composition of the present invention contains (A) epoxy resin.

[0039] Examples of epoxy resins (A) include: 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, triphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, etc. Novolac type epoxy resins include biphenyl type epoxy resins, linear aliphatic epoxy resins, butadiene-structured epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexane type epoxy resins, cyclohexanediethanol type epoxy resins, naphthyl ether type epoxy resins, trimethylolpropionic acid type epoxy resins, tetraphenylethane type epoxy resins, etc. Epoxy resins can be used alone or in combination of two or more.

[0040] In the resin composition, it is preferable that the epoxy resin having two or more epoxy groups per molecule is included as (A) epoxy resin. From the viewpoint of significantly obtaining the desired effect of the present invention, the proportion of epoxy resin having two or more epoxy groups per molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the non-volatile component of (A) epoxy resin.

[0041] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter also referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter also referred to as "solid epoxy resins"). In one embodiment, the resin composition of the present invention comprises a liquid epoxy resin as the epoxy resin. In one embodiment, the resin composition of the present invention comprises a solid epoxy resin as the epoxy resin. The resin composition of the present invention may comprise only a liquid epoxy resin, or it may comprise only a solid epoxy resin, preferably a combination of both liquid and solid epoxy resins.

[0042] As a liquid epoxy resin, it is preferable to be a liquid epoxy resin having two or more epoxy groups in one molecule.

[0043] As liquid epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenolic aldehyde type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanediol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin with butadiene structure are preferred, and glycidylamine type epoxy resin, bisphenol A type epoxy resin, and bisphenol F type epoxy resin are even more preferred.

[0044] Specific examples of liquid epoxy resins include: DIC's "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US", "jER828EL", "825", and "EPIKOTE828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807" and "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "jER152" (phenolic resin); Mitsubishi Chemical's "630" and "630LSD" (glycidylamine type epoxy resin); Nippon Steel & Sumitomo Metal Chemicals' "ZX1059" (a mixture of bisphenol A and bisphenol F type epoxy resin); Nagase ChemteX's "EX-721" (glycidyl ester type epoxy resin); and Daicel's "Celloxide"... 2021P (alicyclic epoxy resin with an ester skeleton); Daicel's "PB-3600"; Nippon Soda's "JP-100" and "JP-200" (epoxy resins with a butadiene structure); Nippon Steel & Sumitomo Chemical's "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin), etc. These can be used individually or in combination of two or more.

[0045] As a solid epoxy resin, it is preferable to be a solid epoxy resin having three or more epoxy groups per molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups per molecule.

[0046] As solid epoxy resins, the preferred types are xylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol-phenolic epoxy resins, dicyclopentadiene-type epoxy resins, triphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins.

[0047] Specific examples of solid epoxy resins include: DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" (cresol-phenolic epoxy resin); DIC's "N-695" (cresol-phenolic epoxy resin); DIC's "HP-7200" (dicyclopentadiene epoxy resin); and DIC's "H"... P-7200HH, HP-7200H, EXA-7311, EXA-7311-G3, EXA-7311-G4, EXA-7311-G4S, HP6000 (naphthyl ether type epoxy resin); EPPN-502H (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; NC7000L (naphthol phenolic resin) manufactured by Nippon Kayaku Co., Ltd.; NC3000H manufactured by Nippon Kayaku Co., Ltd. "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.; "ESN485" (naphthol phenolic type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. These include: epoxy resins such as: Mitsubishi Chemical's "YX8800" (anthracene-type epoxy resin); Osaka Gas Chemical's "PG-100" and "CG-500"; Mitsubishi Chemical's "YL7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical's "YL7800" (fluorene type epoxy resin); Mitsubishi Chemical's "jER1010" (solid bisphenol A type epoxy resin); and Mitsubishi Chemical's "jER1031S" (tetraphenylethane type epoxy resin). These can be used individually or in combination of two or more.

[0048] When using a combination of liquid and solid epoxy resins as (A) epoxy resin, the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, and particularly preferably 5:1 to 1:5. By maintaining the mass ratio of liquid epoxy resin to solid epoxy resin within the aforementioned range, the desired effects of the present invention can be significantly obtained.

[0049] From the viewpoint of significantly achieving the desired effects of the present invention, (A) the epoxy equivalent of the epoxy resin is preferably 50 g / eq. or more, more preferably 70 g / eq. or more. On the other hand, from the viewpoint of significantly achieving the desired effects of the present invention, the epoxy equivalent is preferably 5000 g / eq. or less, more preferably 2000 g / eq. or less, further preferably 1000 g / eq. or less, further preferably 500 g / eq. or less, even more preferably 400 g / eq. or less, and particularly preferably 350 g / eq. or less. Epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be determined according to JIS K7236.

[0050] From the viewpoint of significantly achieving the desired effects of the present invention, (A) the weight-average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. The weight-average molecular weight of the resin can be determined by gel permeation chromatography (GPC) as a value converted from polystyrene.

[0051] (A) The content of epoxy resin is not particularly limited. When the resin component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and particularly preferably 45% by mass or more. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and particularly preferably 60% by mass or less.

[0052] It should be noted that in this specification, "resin composition" refers to the non-volatile components constituting the resin composition other than the inorganic filler material (C) described later.

[0053] When liquid epoxy resin is included, the content of liquid epoxy resin is not particularly limited. From the viewpoint of significantly obtaining the desired effect of the present invention, when the resin component in the resin composition is set to 100% by mass, it is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and particularly preferably 30% by mass or more. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and particularly preferably 60% by mass or less.

[0054] When solid epoxy resin is included, the content of solid epoxy resin is not particularly limited. However, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferable to have 1% or more by mass when the resin component in the resin composition is set to 100% by mass; more preferably, 5% or more by mass; further preferably, 10% or more by mass; and particularly preferably, 15% or more by mass. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit is preferably 40% or less by mass; more preferably, 30% or less by mass; further preferably, 25% or less by mass; and particularly preferably, 20% or less by mass.

[0055] <(B) Curing Agent>

[0056] The resin composition of the present invention contains (B) a curing agent.

[0057] As for the (B) curing agent, there is no particular limitation as long as it has the function of curing epoxy resin. Examples include: phenolic curing agents, naphthol curing agents, acid anhydride curing agents, reactive ester curing agents, benzoxazine curing agents, cyanate ester curing agents, and carbodiimide curing agents. A single curing agent can be used, or two or more can be used in combination. From the viewpoint of significantly obtaining the desired effects of the present invention, the (B) curing agent of the resin composition of the present invention preferably includes a phenolic curing agent or an acid anhydride curing agent.

[0058] From the viewpoint of heat resistance and water resistance, phenolic curing agents or naphthol curing agents with a phenolic (novolac, linear phenolic) structure are preferred as curing agents. Furthermore, from the viewpoint of adhesion to the adhered materials, nitrogen-containing phenolic or naphthol curing agents are preferred, and phenolic or naphthol curing agents containing a triazine skeleton are even more preferred. Among these, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, phenolic resins containing a triazine skeleton are preferred. Specific examples of phenolic and naphthol-based curing agents include: MEH-7700, MEH-7810, MEH-7851 manufactured by Meiwa Chemical Co., Ltd.; NHN, CBN, GPH manufactured by Nippon Chemical Co., Ltd.; SN-170, SN-180, SN-190, SN-475, SN-485, SN-495, SN-375, SN-395 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; and LA-7052, LA-7054, LA-3018, LA-3018-50P, LA-1356, TD2090 manufactured by DIC Co., Ltd.

[0059] Anhydride-based curing agents can be categorized as curing agents having one or more anhydride groups within a single molecule. Specific examples of anhydride-based curing agents include: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, and pyromellitic anhydride. Anhydrides include benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic anhydride, 3,3'-4,4'-diphenyl sulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(triphenylamine), and styrene-maleic acid resin copolymerized with styrene and maleic acid, among other polymeric anhydrides. Commercially available anhydride-based curing agents include "HNA-100" and "MH-700" manufactured by Shin Nippon Rikka Co., Ltd.

[0060] There are no particular limitations on the active ester-based curing agent used, but it is generally preferable to use compounds with two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, and heterocyclic hydroxyl compounds. This active ester-based curing agent is preferably obtained through a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenolic compound and / or a naphthol compound is even more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenolic or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyroglucinol, dicyclopentadiene-type diphenol compounds, and phenolic resins. The term "dicyclopentadiene-type diphenol compound" here refers to a diphenol compound obtained by the condensation of one molecule of dicyclopentadiene with two molecules of phenol.

[0061] Specifically, the preferred active ester compounds are those containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated form of phenolic resin, and active ester compounds containing a benzoyl form of phenolic resin. More preferably, these are active ester compounds containing a naphthalene structure or active ester compounds containing a dicyclopentadiene-type diphenol structure. The term "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit formed from a phenylene-dicyclopentylene-phenylene group.

[0062] Commercially available reactive ester-based curing agents include reactive ester compounds with a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", and "EXB-8000L-65TM" (manufactured by DIC); and reactive ester compounds with a naphthalene structure, such as "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC). Examples of active ester compounds containing acetylated phenolic resins include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester compounds containing benzoylated phenolic resins include "YLH1026" (manufactured by Mitsubishi Chemical Corporation); examples of active ester curing agents for acetylated phenolic resins include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester curing agents for benzoylated phenolic resins include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); etc.

[0063] Specific examples of benzoxazine-based curing agents include: "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemical Co., Ltd.

[0064] Examples of cyanate ester curing agents include: bisphenol A dicyanate, polyphenol cyanates (oligomeric (3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate-phenylpropane), 1,1-bis(4-cyanate-phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate-phenyl-1-(methylethylene))benzene, bis(4-cyanate-phenyl) sulfide, and bis(4-cyanate-phenyl) ether, etc., difunctional cyanate ester resins, polyfunctional cyanate ester resins derived from phenolic resins and cresol resins, and prepolymers obtained by partially triazinizing these cyanate ester resins, etc. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (both phenolic phenolic polyfunctional cyanate ester resins), "BA230", and "BA230S75" (prepolymers formed by triazinizing part or all of bisphenol A dicyanate to form a trimer).

[0065] Specific examples of carbodiimide-based curing agents include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

[0066] When a curing agent is included, the ratio of epoxy resin to curing agent, expressed as [total number of epoxy groups in the epoxy resin] : [total number of reactive groups in the curing agent], is preferably in the range of 1:0.2 to 1:2, more preferably in the range of 1:0.3 to 1:1.5, and even more preferably in the range of 1:0.4 to 1:1.2. Here, the reactive groups of the curing agent are active hydroxyl groups, active ester groups, etc., depending on the type of curing agent. Furthermore, the total number of epoxy groups in the epoxy resin refers to the sum of values ​​obtained by dividing the mass of the non-volatile component of each epoxy resin by the epoxy equivalent for all epoxy resins; the total number of reactive groups in the curing agent refers to the sum of values ​​obtained by dividing the mass of the non-volatile component of each curing agent by the reactive group equivalent for all curing agents. By keeping the ratio of epoxy resin to curing agent within the above range, the heat resistance of the resulting cured product can be further improved.

[0067] (B) The content of the curing agent is not particularly limited. From the viewpoint of significantly obtaining the desired effect of the present invention, when the resin component in the resin composition is set to 100% by mass, it is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 25% by mass or more. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit is preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, and particularly preferably 35% by mass or less.

[0068] <(C) Inorganic filler materials>

[0069] The resin composition of the present invention may, as an optional component, further contain (C) inorganic filler material.

[0070] (C) The inorganic filler material is not particularly limited, but examples include: silicon dioxide, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silicon dioxide is particularly preferred. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, etc. Furthermore, spherical silicon dioxide is preferred. One type of inorganic filler material may be used alone, or two or more may be used in combination.

[0071] Commercially available products as (C) inorganic filler materials include, for example: "UFP-30" manufactured by Denka Kagaku Kogyo Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Co., Ltd.; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; etc.

[0072] From the viewpoint of significantly achieving the desired effects of the present invention, (C) the average particle size of the inorganic filler material is preferably 30 μm or less, more preferably 20 μm or less, further preferably 15 μm or less, even more preferably 12 μm or less, and particularly preferably 10 μm or less. From the viewpoint of significantly achieving the desired effects of the present invention, the lower limit of the average particle size of the inorganic filler material is preferably 0.1 μm or more, more preferably 1 μm or more, further preferably 2 μm or more, and particularly preferably 2.5 μm or more. Especially in the case of resin sheet morphology, 2.5 μm or more is preferred. The average particle size of the inorganic filler material can be determined by laser diffraction scattering based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler material can be prepared on a volume basis using a laser diffraction scattering particle size distribution measuring device, and the median particle size can be used as the average particle size for measurement. The sample for measurement can be a sample obtained by weighing 100 mg of inorganic filler material and 10 g of methyl ethyl ketone into a tube and dispersing it ultrasonically for 10 minutes. For the sample being measured, a laser diffraction particle size distribution measuring device is used, employing blue and red light source wavelengths. The particle size distribution of the inorganic filler material is measured using a flow cell method based on a volume reference, and the average particle size is calculated from the obtained particle size distribution as the median particle size. Examples of laser diffraction particle size distribution measuring devices include the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0073] From the perspective of improving moisture resistance and dispersibility, (C) the inorganic filler material is preferably treated with one or more surface treatment agents selected from aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, titanate coupling agents, etc. Commercially available surface treatment agents include, for example: KBM403 (3-epoxypropoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM803 (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBE903 (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM573 (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., SZ-31 (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM103 (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM-4803 (long-chain epoxy silane coupling agent) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and KBM-7103 (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0074] From the perspective of improving the dispersibility of inorganic fillers, the degree of surface treatment using surface treatment agents is preferably within a specified range. Specifically, it is preferable to surface treat 100 parts by mass of inorganic filler with 0.2 to 5 parts by mass of surface treatment agent, more preferably with 0.2 to 3 parts by mass of surface treatment agent, and even more preferably with 0.3 to 2 parts by mass of surface treatment agent.

[0075] The degree of surface treatment using surface treatment agents can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the perspective of improving the dispersibility of the inorganic filler, a carbon content per unit surface area of ​​0.02 mg / m² is preferable. 2 The above is better, preferably 0.1 mg / m². 2 The above, and even better, is 0.2 mg / m². 2 That's all. On the other hand, from the viewpoint of suppressing the increase in melt viscosity of the resin varnish and melt viscosity in sheet form, 1 mg / m³ is preferable. 2 The following is preferable: 0.8 mg / m² 2 The following is even better: 0.5 mg / m² 2 the following.

[0076] (C) The carbon content per unit surface area of ​​the inorganic filler material can be determined after cleaning the surface-treated inorganic filler material with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, sufficient MEK is added as a solvent to the surface-treated inorganic filler material, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler material can be determined using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba Corporation can be used.

[0077] From the viewpoint of further improving the effect of the present invention, (C) the specific surface area of ​​the inorganic filler material is preferably 1m². 2 / g or higher, preferably 1.5m 2 / g or higher, especially 2m 2 / g or more. There is no particular upper limit, but 50mg is preferred. 2 / g or less, 45m 2 / g or less or 40m 2 / g or less. The specific surface area of ​​inorganic filler materials can be obtained as follows: according to the BET method, nitrogen gas is adsorbed onto the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech), and the specific surface area is calculated using the BET multi-point method.

[0078] In the case of containing inorganic filler (C), the content of inorganic filler (C) is not particularly limited. From the viewpoint of significantly obtaining the desired effect of the present invention, when the non-volatile component in the resin composition is set to 100% by mass, it is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 83% by mass or more, and particularly preferably 85% by mass or more. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 88% by mass or less.

[0079] <(D) Elastomer>

[0080] The resin composition of the present invention may further contain (D) an elastomer as an optional component.

[0081] In this invention, (D) elastomer refers to a resin with flexibility, which is an amorphous resin component dissolved in an organic solvent, preferably a resin that exhibits rubber elasticity by polymerization with a resin or other components that have rubber elasticity. Examples of such resins include those that, as rubber elasticity, exhibit an elastic modulus of less than 1 GPa when subjected to a tensile test at 25°C and 40% RH according to Japanese Industrial Standard (JIS K7161).

[0082] In one embodiment, component (D) is preferably a resin having one or more structures selected from polybutadiene, polysiloxane, poly(meth)acrylate, polyalkylene, polyalkyleneoxy, polyisoprene, polyisobutylene, and polycarbonate structures within its molecule. From the viewpoint of further maximizing the desired effects of the invention, it is more preferably a resin having one or more structures selected from polybutadiene and polycarbonate structures. It should be noted that "(meth)acrylate" refers to methacrylates and acrylates.

[0083] In another embodiment, component (D) is preferably selected from one or more resins having a glass transition temperature (Tg) of 25°C or lower and resins that are liquid at 25°C or lower. The glass transition temperature of the resin having a Tg of 25°C or lower is preferably 20°C or lower, more preferably 15°C or lower. There is no particular limitation on the lower limit of the glass transition temperature; it can generally be -15°C or higher. Furthermore, as for the resin that is liquid at 25°C, it is preferable to have a resin that is liquid at 20°C or lower, more preferably a resin that is liquid at 15°C or lower.

[0084] As a more preferred embodiment, (D) component is preferably a resin selected from one or more resins with a glass transition temperature of 25°C or below and which are liquid at 25°C, and which has a structure selected from one or more of polybutadiene, polysiloxane, poly(meth)acrylate, polyalkylene, polyalkyleneoxy, polyisoprene, polyisobutylene, and polycarbonate structures within its molecules.

[0085] The polybutadiene structure includes not only structures formed by polymerizing butadiene, but also structures formed by hydrogenating the butadiene. Furthermore, the butadiene structure can be partially or completely hydrogenated. Additionally, component (D) can contain polybutadiene structures in the main chain or in the side chains.

[0086] Preferred examples of polybutadiene resins include: resins containing a hydrogenated polybutadiene backbone, polybutadiene resins containing hydroxyl groups, polybutadiene resins containing phenolic hydroxyl groups, polybutadiene resins containing carboxyl groups, polybutadiene resins containing acid anhydride groups, polybutadiene resins containing epoxy groups, polybutadiene resins containing isocyanate groups, and polybutadiene resins containing urethane groups. Among these, polybutadiene resins containing phenolic hydroxyl groups are particularly preferred. The term "resin containing a hydrogenated polybutadiene backbone" refers to a resin in which at least a portion of the polybutadiene backbone is hydrogenated, and does not necessarily mean that the polybutadiene backbone is completely hydrogenated. Examples of resins containing a hydrogenated polybutadiene backbone include, for example, epoxy resins containing a hydrogenated polybutadiene backbone. Furthermore, examples of polybutadiene resins containing phenolic hydroxyl groups include resins having a polybutadiene structure and containing phenolic hydroxyl groups.

[0087] Specific examples of resins containing an intramolecular polybutadiene structure, i.e., polybutadiene resins, include: "Ricon 657" (polybutadiene containing epoxy groups), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", and "Ricon..." manufactured by CrayValley. 184MA6 (polybutadiene containing anhydride groups), "GQ-1000" (polybutadiene with introduced hydroxyl and carboxyl groups), "G-1000", "G-2000", "G-3000" (polybutadiene with two-terminated hydroxyl groups), "GI-1000", "GI-2000", "GI-3000" (hydrogenated polybutadiene with two-terminated hydroxyl groups), "PB3600" and "PB4700" (polybutadiene skeleton epoxy compounds) manufactured by Daicel, "EPOFRIEND A1005", "EPOFRIEND A1010", "EPOFRIEND A1020" (epoxide compounds of styrene-butadiene-styrene block copolymers), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy compounds) manufactured by NagaseChemteX, "R-45EPT" (polybutadiene skeleton epoxy compounds), etc.

[0088] Furthermore, as a preferred example of a polybutadiene resin, linear polyimides (as described in Japanese Patent Application Publication No. 2006-37083 and International Publication No. 2008 / 153208) made from hydroxyl-terminated polybutadiene, diisocyanate compounds, and polybasic acids or their anhydrides can also be cited. The polybutadiene content of this polyimide resin is preferably 60% to 95% by mass, and more preferably 75% to 85% by mass. For details regarding this polyimide resin, please refer to the descriptions in Japanese Patent Application Publication No. 2006-37083 and International Publication No. 2008 / 153208, the contents of which are incorporated herein by reference.

[0089] From the viewpoint of achieving the desired effects of the present invention, the number average molecular weight of the hydroxyl-terminated polybutadiene is preferably 500 to 5,000, more preferably 1,000 to 3,000. From the viewpoint of achieving the desired effects of the present invention, the hydroxyl equivalent of the hydroxyl-terminated polybutadiene is preferably 250 to 1,250.

[0090] Examples of diisocyanate compounds include: aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene diisocyanate, and diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate. Aromatic diisocyanates are preferred, and toluene-2,4-diisocyanate is more preferred.

[0091] Examples of polybasic acids or their anhydrides include: ethylene glycol bis(triphenylene oxide), pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, naphthalene tetracarboxylic acid, tetracarboxylic acids such as 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-cyclohexene-1,2-dicarboxylic acid and 3,3'-4,4'-diphenylsulfone tetracarboxylic acid and their anhydrides, tribasic acids such as trimellitic acid and cyclohexane tricarboxylic acid and their anhydrides, and 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho(1,2-C)furan-1,3-dione, etc.

[0092] A polysiloxane structure is a structure containing siloxane bonds, such as that contained in silicone rubber. (D) In ​​the composition, a polysiloxane structure can be contained in the main chain or in the side chain.

[0093] Specific examples of resins with an intramolecular polysiloxane structure, namely polysiloxane resins, include: "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone, and linear polyimide (International Publication No. 2010 / 053185) made from amino-terminated polysiloxanes and tetrabasic anhydrides.

[0094] The poly(meth)acrylate structure is a structure formed by polymerizing acrylic acid or acrylate, and also includes structures formed by polymerizing methacrylic acid or methacrylate. In component (D), the (meth)acrylate structure may be included in the main chain or in the side chain.

[0095] Preferred examples of resins having a poly(meth)acrylate structure within the molecule, i.e., poly(meth)acrylate resins, include: poly(meth)acrylate resins containing hydroxyl groups, poly(meth)acrylate resins containing phenolic hydroxyl groups, poly(meth)acrylate resins containing carboxyl groups, poly(meth)acrylate resins containing anhydride groups, poly(meth)acrylate resins containing epoxy groups, poly(meth)acrylate resins containing isocyanate groups, and poly(meth)acrylate resins containing urethane groups, etc.

[0096] Specific examples of poly(meth)acrylate resins include: TEISANRESIN “SG-70L”, “SG-708-6”, “WS-023”, “SG-700AS”, “SG-280TEA” (carboxyl-containing acrylate copolymer resins with acid values ​​of 5–34 mg KOH / g, weight-average molecular weights of 400,000–900,000, and Tg values ​​of -30℃–5℃), “SG-80H”, “SG-80H-3”, and “SG-P3” (epoxy-containing acrylate copolymer resins with epoxy equivalents of 4761–14285 g / eq and weight-average molecular weights of 350,000). (e.g., 850,000, Tg 11℃~12℃), “SG-600TEA”, “SG-790” (hydroxyl-containing acrylate copolymer resin, hydroxyl value 20~40mgKOH / g, weight average molecular weight 500,000~1,200,000, Tg -37℃~-32℃), “ME-2000”, “W-116.3” (carboxyl-containing acrylate copolymer resin), “W-197C” (hydroxyl-containing acrylate copolymer resin), “KG-25”, “KG-3000” (epoxy-containing acrylate copolymer resin), etc. manufactured by Negami Kogyo Co., Ltd.

[0097] The polyalkylene structure preferably has a specified number of carbon atoms. Specifically, the polyalkylene structure preferably has 2 or more carbon atoms, more preferably 3 or more, particularly preferably 5 or more, preferably 15 or less, more preferably 10 or less, and particularly preferably 6 or less. Furthermore, in component (D), the polyalkylene structure may be included in the main chain or in the side chain.

[0098] The polyalkylene oxide structure preferably has a specified number of carbon atoms. Specifically, the polyalkylene oxide structure preferably has 2 or more carbon atoms, more preferably 3 or more, more preferably 5 or more, more preferably 15 or less, more preferably 10 or less, and particularly preferably 6 or less. (D) The polyalkylene oxide structure may be included in the main chain or in the side chain of the component.

[0099] Specific examples of resins containing polyalkylene structures within the molecule, namely polyalkylene resins, and resins containing polyalkyleneoxy structures within the molecule, namely polyalkyleneoxy resins, include: Asahi Kasei Corporation's "PTXG-1000" and "PTXG-1800", Mitsubishi Chemical Corporation's "YX-7180" (containing resins with alkylene structures having ether bonds), DIC Corporation's "EXA-4850-150", "EXA-4816", and "EXA-4822", ADEKA Corporation's "EP-4000", "EP-4003", "EP-4010", and "EP-4011", Shin Nippon Rikka Corporation's "BEO-60E" and "BPO-20E", and Mitsubishi Chemical Corporation's "YL7175" and "YL7410", etc.

[0100] (D) In ​​this component, polyisoprene structures can be included in the main chain or in the side chains. Specific examples of resins containing polyisoprene structures within the molecule, i.e., polyisoprene resins, include "KL-610" and "KL-613" manufactured by Kuraray Co., Ltd.

[0101] (D) The main chain may contain polyisobutylene structures, or the side chains may contain polyisobutylene structures. Specific examples of resins containing polyisobutylene structures within the molecule, i.e., polyisobutylene resins, include: KANEKA's "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer), etc.

[0102] (D) In ​​the component, polycarbonate structure can be included in the main chain or in the side chain.

[0103] Preferred examples of polycarbonate resins having a polycarbonate structure within the molecule include: polycarbonate resins containing hydroxyl groups, polycarbonate resins containing phenolic hydroxyl groups, polycarbonate resins containing carboxyl groups, polycarbonate resins containing anhydride groups, polycarbonate resins containing epoxy groups, polycarbonate resins containing isocyanate groups, and polycarbonate resins containing urethane groups.

[0104] Specific examples of polycarbonate resins include Asahi Kasei Chemicals' "T6002" and "T6001" (polycarbonate diol), and Kuraray's "C-1090", "C-2090", and "C-3090" (polycarbonate diol).

[0105] Furthermore, as preferred examples of polycarbonate resins, linear polyimides made from hydroxyl-terminated polycarbonates, diisocyanate compounds, and polybasic acids or their anhydrides can be cited. These linear polyimides have both urethane and polycarbonate structures. The polycarbonate content of this polyimide resin is preferably 60% to 95% by mass, and more preferably 75% to 85% by mass. For details regarding this polyimide resin, please refer to International Publication No. 2016 / 129541, the contents of which are incorporated herein by reference.

[0106] From the viewpoint of achieving the desired effects of the present invention, the number average molecular weight of the hydroxyl-terminated polycarbonate is preferably 500 to 5,000, more preferably 1,000 to 3,000. From the viewpoint of achieving the desired effects of the present invention, the hydroxyl equivalent of the hydroxyl-terminated polycarbonate is preferably 250 to 1,250.

[0107] Component (D) is better if it further possesses an imide structure. By possessing an imide structure, the heat resistance of component (D) can be improved, and its crack resistance can be effectively enhanced.

[0108] (D) The component can be any structure among linear, branched and cyclic, but from the viewpoint of achieving the desired effect of the present invention, it is preferably linear.

[0109] Component (D) preferably also has functional groups that can react with component (A). These functional groups may also include reactive groups that appear upon heating. By giving component (D) functional groups, the mechanical strength of the cured resin composition can be improved.

[0110] Examples of functional groups include carboxyl, hydroxyl, acid anhydride, phenolic hydroxyl, epoxy, isocyanate, and carbamate groups. From the viewpoint of significantly achieving the effects of the present invention, it is preferable that the functional group has one or more functional groups selected from hydroxyl, acid anhydride, phenolic hydroxyl, epoxy, isocyanate, and carbamate groups, with phenolic hydroxyl being particularly preferred.

[0111] (D) Components may be used alone or in combination of two or more.

[0112] From the viewpoint of achieving the desired effects of the present invention, component (D) is preferably of high molecular weight. Specifically, the number-average molecular weight Mn of component (D) is preferably 4000 or more, more preferably 4500 or more, further preferably 5000 or more, particularly preferably 5500 or more, preferably 100000 or less, more preferably 95000 or less, and particularly preferably 90000 or less. By ensuring that the number-average molecular weight Mn of component (D) is within the aforementioned range, the desired effects of the present invention can be significantly obtained. The number-average molecular weight Mn of component (D) is the number-average molecular weight converted to polystyrene, determined using GPC (gel permeation chromatography).

[0113] Furthermore, from the viewpoint of significantly achieving the desired effects of the present invention, the specific weight-average molecular weight of component (D) is preferably 5,500 to 100,000, more preferably 10,000 to 90,000, and even more preferably 15,000 to 80,000. The weight-average molecular weight of component (D) is the weight-average molecular weight converted to polystyrene by gel permeation chromatography (GPC).

[0114] When component (D) has functional groups, the functional group equivalent of component (D) is preferably 100 or more, more preferably 200 or more, further preferably 1000 or more, particularly preferably 2500 or more, preferably 50000 or less, more preferably 30000 or less, further preferably 10000 or less, and particularly preferably 5000 or less. Functional group equivalent is the number of grams of resin containing 1 gram equivalent of functional groups. For example, the epoxy equivalent can be determined according to JIS K7236. Alternatively, for example, the hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value determined according to JIS K1557-1.

[0115] When the (D) elastomer is included, the content of the (D) elastomer is not particularly limited. From the viewpoint of significantly obtaining the desired effect of the present invention, when the resin component in the resin composition is set to 100% by mass, it is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and particularly preferably 9% by mass or more. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less.

[0116] <(E) Rubber Particles>

[0117] The resin composition of the present invention may, as an optional component, further contain (E) rubber particles.

[0118] The resin composition contains (E) rubber particles. The (E) rubber particles of this invention are manufactured by increasing the molecular weight of the rubber component to a level insoluble in organic solvents and resin components, and forming particles. Therefore, the rubber particles are insoluble in organic solvents and incompatible with other components such as epoxy resins or curing agents, and thus can exist in a dispersed state in resin varnishes and resin compositions. They typically function as an organic filler with rubber elasticity. By containing these (E) rubber particles, the adhesion of the cured resin composition at low temperatures can be improved. Furthermore, by including the (E) component in the resin composition, tackiness can be reduced, and the workability of the cured resin composition can be improved. Moreover, by utilizing the (E) component, the elastic modulus of the insulation layer can typically be reduced, or the resistance to elongation can be improved.

[0119] Examples of (E) rubber particles include: core-shell rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, acrylic rubber particles, etc. Among these, core-shell rubber particles are preferred from the viewpoint of significantly achieving the desired effects of the present invention.

[0120] Core-shell rubber particles are rubber particles comprising a shell layer on the surface of the particle and a core layer inside the shell layer. Examples include core-shell rubber particles comprising a shell layer formed of a polymer with a relatively high glass transition temperature and a core layer formed of a polymer with a relatively low glass transition temperature. Preferably, the shell layer is formed of a glassy polymer and the core layer is formed of a rubbery polymer. Such core-shell rubber particles utilize the shell layer to inhibit the aggregation of rubber particles or improve the dispersibility of rubber particles in resin components, and utilize the core layer to exhibit excellent rubber elasticity. Core-shell rubber particles can be manufactured, for example, by seeding and polymerizing one or more monomers corresponding to each layer in multiple stages.

[0121] Core-shell rubber particles can have a two-layer structure consisting only of a shell and a core, or they can have a structure with three or more layers containing any further arbitrary layers. For example, core-shell rubber particles can contain any layer between the shell and the core, or any layer inside the core. Specifically, a core-shell rubber particle can have a three-layer structure comprising: a shell formed of a glassy polymer, a core formed of a rubbery polymer, and any layer formed of a glassy polymer inside the core.

[0122] Among the aforementioned core-shell rubber particles, examples of glassy polymers include: acrylic polymers such as polymethyl methacrylate; styrene polymers such as polystyrene, polymethyl methacrylate-styrene copolymers, and styrene-divinylbenzene copolymers; etc. Of these, acrylic polymers are preferred, and polymethyl methacrylate is particularly preferred. On the other hand, examples of rubbery polymers include: acrylic rubbers such as homopolymers or copolymers of acrylic monomers such as butyl acrylate; butadiene rubbers such as polybutadiene and butadiene-styrene copolymers; isoprene rubber; butyl rubber; etc. Of these, acrylic rubbers and butadiene rubbers are preferred, and acrylic rubbers are particularly preferred. Here, the term "acrylic monomers" includes acrylates, methacrylates, and combinations thereof.

[0123] Specific examples of core-shell rubber particles include: STAPHYLOID “AC3832”, “AC3816N”, and “IM401-modified 7-17” manufactured by AICA Industries; “METABLEN KW-4426” manufactured by Mitsubishi Chemical Corporation; and PARALOID “EXL-2655” manufactured by Dow Chemical Japan.

[0124] Specific examples of crosslinked acrylonitrile butadiene rubber (NBR) particles include JSR's "XER-91" (average particle size 0.5 μm); etc. Specific examples of crosslinked styrene butadiene rubber (SBR) particles include JSR's "XSK-500" (average particle size 0.5 μm); etc. Specific examples of acrylic rubber particles include Mitsubishi Chemical's METABLEN "W300A" (average particle size 0.1 μm) and "W450A" (average particle size 0.2 μm); etc.

[0125] (E) One type of rubber particle may be used alone, or two or more may be used in combination.

[0126] (E) rubber particles typically enhance the toughness of cured resin compositions. Therefore, insulating layers formed from cured resin compositions containing (E) rubber particles exhibit superior mechanical strength. Furthermore, (E) rubber particles generally possess stress relaxation properties. Thus, the internal stress generated during the formation of an insulating layer from a cured resin composition containing (E) rubber particles is relaxed due to the (E) rubber particles. This reduces residual stress in the insulating layer, thereby further improving its mechanical strength and suppressing embrittlement. Consequently, delamination (peeling) of the insulating layer is suppressed even at low temperatures.

[0127] (E) The average particle size of the rubber particles is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 1 μm or less, and more preferably 0.6 μm or less. (E) The average particle size of the rubber particles can be determined using dynamic light scattering. Specifically, the rubber particles are uniformly dispersed in a suitable organic solvent using methods such as ultrasound, and the particle size distribution of the rubber particles is prepared using a concentrated particle size analyzer (Otsuka Electronics Co., Ltd. "FPAR-1000") based on mass, and the median particle size is used as the average particle size for determination.

[0128] When (E) rubber particles are included, the content of (E) rubber particles is not particularly limited. From the viewpoint of significantly obtaining the desired effect of the present invention, when the resin component in the resin composition is set to 100% by mass, it is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0129] <(F) Curing Accelerator>

[0130] The resin composition of the present invention may, as an optional component, further contain (F) a curing accelerator.

[0131] Examples of (F) curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among these, phosphorus-based, amine-based, imidazole-based, and metal-based curing accelerators are preferred, and phosphorus-based and imidazole-based curing accelerators are even more preferred. A single curing accelerator may be used alone, or two or more may be used in combination.

[0132] Examples of phosphorus-based curing accelerators include: triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, methyltributylphosphonium dimethyl phosphate, etc.

[0133] Examples of amine-based curing accelerators include triethylamine, tributylamine and other trialkylamines, 4-dimethylaminopyridine (DMAP), benzyl dimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]undecene, etc.

[0134] Examples of imidazole-based curing accelerators include: 2-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolium-(1')] [Ethyl-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds with epoxy resins.

[0135] As an imidazole-based curing accelerator, commercially available products can be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0136] Examples of guanidine-based curing accelerators include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, 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-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, etc.

[0137] Examples of organometallic curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include: cobalt(II) acetylacetone, cobalt(III) acetylacetone, copper(II) acetylacetone, zinc(II) acetylacetone, iron(III) acetylacetone, nickel(II) acetylacetone, and manganese(II) acetylacetone. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0138] When the (F) curing accelerator is included, the content of the (F) curing accelerator is not particularly limited. From the viewpoint of significantly obtaining the desired effect of the present invention, when the resin component in the resin composition is set to 100% by mass, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, and particularly preferably 0.4% by mass or more. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 2% by mass or less, and particularly preferably 1% by mass or less.

[0139] <(G) Organic Solvents>

[0140] The resin composition of the present invention may, as an optional component, further contain (G) an organic solvent.

[0141] Examples of organic solvents include: ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, acetic acid cellosolve, propylene glycol monomethyl ether acetate, carbitol acetate, and diethylene glycol monoethyl ether acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. Organic solvents can be used alone or in combination of two or more in any ratio.

[0142] When the (G) organic solvent is present, the content of the (G) organic solvent is not particularly limited. From the viewpoint of obtaining the desired effect of the present invention, when the total resin composition is set to 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less. The lower limit is not particularly limited.

[0143] <(H) Other Additives>

[0144] In addition to the components described above, the resin composition may further include other additives as optional components. Examples of such additives include, for instance, thermoplastic resins, adhesives, flame retardants, thickeners, defoamers, leveling agents, organometallic compounds, colorants, adhesion promoters, and other resin additives; polymerization initiators, etc. These additives may be used individually or in combination of two or more. Those skilled in the art can appropriately determine their respective contents.

[0145] <Method for manufacturing resin composition>

[0146] The resin composition of the present invention can be manufactured by stirring the compounding components, for example, using a stirring device such as a rotary mixer, to disperse them uniformly.

[0147] <Characteristics of the Resin Composition>

[0148] The resin composition of the present invention has the following characteristic: the oxygen permeability coefficient of the cured product obtained by heat curing it at 180°C for 90 minutes is 3cc / (atm·m). 2 (·day·mm). Regarding the oxygen permeability coefficient, it is calculated by measuring the oxygen permeability of the cured product obtained by heat curing the resin composition of the present invention at 180°C for 90 minutes, and dividing that value by the thickness of the cured product. The methods described in the examples can be used specifically as the methods for measuring the oxygen permeability and calculating the oxygen permeability coefficient. The oxygen permeability coefficient of the cured product obtained by heat curing at 180°C for 90 minutes is preferably 2.5 cc / (atm·mm). 2 Below 2.0cc / (atm·mm), 2.0cc / (atm·mm) is better. 2 Below 1.5cc / (atm·mm), further preferably 1.5cc / (atm·mm) 2 Below 0.01 cc / (atm·mm). There is no particular limit to the lower limit, but it is generally preferred to be 0.01 cc / (atm·mm). 2 ·day·mm) or more, preferably 0.2cc / (atm·m) 2 ·day·mm) or above.

[0149] The resin composition of the present invention is characterized in that the coefficient of linear thermal expansion of the cured product obtained by heat curing it at 180°C for 90 minutes is 4 to 15 ppm / °C. The method described in the examples can be used as the determination method. Preferably, the coefficient of linear thermal expansion of the cured product obtained by heat curing the resin composition of the present invention at 180°C for 90 minutes is 12 ppm / °C or less, more preferably 10 ppm / °C or less, and even more preferably 8.5 ppm / °C or less. The lower limit is preferably 3.5 ppm / °C or more, more preferably 4.5 ppm / °C or more, and even more preferably 5.5 ppm / °C or more.

[0150] Those skilled in the art know that the coefficient of linear thermal expansion and the oxygen permeability coefficient can typically be adjusted by the types or amounts of the components that may be included in the resin composition.

[0151] Regarding the resin composition of the present invention, by keeping the oxygen permeability coefficient and the coefficient of linear thermal expansion within the aforementioned range, a cured product in which embrittlement and warpage are suppressed can be obtained. Here, regarding embrittlement, the reduction in elongation at high temperature is used as an indicator.

[0152] Specifically, according to the resin composition of the present invention, using the resin composition, a cured resin composition is formed on a 12-inch silicon wafer based on the method described in the examples to prepare a sample substrate. When the sample substrate is heated and cooled in sequence at 35°C, 260°C and 35°C, the warpage measured by the method described in the examples is preferably less than 2.0 mm, more preferably less than 1.5 mm, and even more preferably less than 1.0 mm.

[0153] Furthermore, according to the resin composition of the present invention, the ratio of "elongation at 23°C as measured according to JIS K7127 of the cured product obtained by heat curing at 180°C for 24 hours" to "elongation at 23°C as measured according to JIS K7127 of the cured product obtained by heat curing at 180°C for 90 minutes" is preferably 0.70 or more, more preferably 0.73 or more, and even more preferably 0.75 or more.

[0154] <Uses of Resin Compositions>

[0155] The cured resin composition of the present invention, due to the advantages described above, can be used as a sealing layer and an insulating layer for semiconductors. Therefore, this resin composition can be used as a resin composition for semiconductor sealing or insulating layers.

[0156] For example, the resin composition of the present invention can be suitably used as: a resin composition for forming an insulating layer of a semiconductor chip package (a resin composition for an insulating layer of a semiconductor chip package), and a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) (a resin composition for an insulating layer of a circuit board).

[0157] Furthermore, the resin composition of the present invention can be suitably used, for example, as a resin composition for sealing semiconductor chips in semiconductor chip packages (resin composition for sealing semiconductor chips).

[0158] Examples of semiconductor chip packages for which a sealing or insulating layer can be formed from a cured resin composition of the present invention include: FC-CSP, MIS-BGA package, ETS-BGA package, Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), and Fan-in type PLP.

[0159] Furthermore, the resin composition of the present invention can be used as an underfill material, for example, as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate.

[0160] Furthermore, the resin composition of the present invention can be used in a wide range of applications, including resin sheets, sheet-like laminates such as prepregs, liquid materials such as resin inks for use with solder resists, chip bonding materials, via-filling resins, component embedding resins, etc.

[0161] <Resin Ink (Resin Varnish)>

[0162] The resin ink of the present invention comprises a resin composition. By including an organic solvent in the components of the resin composition, the viscosity can be adjusted and the coatability improved.

[0163] The resin ink of the present invention can be used, for example, as a solder resist ink applied to circuit boards such as printed wiring boards. During coating, a coating apparatus such as a die coater can be used. The thickness of the resin ink layer formed by coating is preferably 600 μm or less, more preferably 500 μm or less. The lower limit of the resin ink layer thickness is preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, further preferably 50 μm or more, and particularly preferably 100 μm or more.

[0164] Furthermore, the resin ink of the present invention can be used to obtain a cured product with a thickness of preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, further preferably 50 μm or more, and particularly preferably 100 μm or more.

[0165] <Resin Sheets>

[0166] The resin sheet of the present invention has a support and a resin composition layer disposed on the support. The resin composition layer is a layer containing the resin composition of the present invention, and is generally formed of the resin composition.

[0167] From the perspective of thinness, the thickness of the resin composition layer is preferably less than 600 μm, more preferably less than 500 μm. The lower limit of the resin composition layer thickness is preferably more than 1 μm, more than 5 μm, more preferably more than 10 μm, further preferably more than 50 μm, and particularly preferably more than 100 μm.

[0168] Furthermore, the thickness of the cured product obtained by curing the resin composition layer is preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, even more preferably 50 μm or more, and particularly preferably 100 μm or more.

[0169] Examples of supports include films made of plastic materials, metal foils, and release paper, with films and metal foils made of plastic materials being preferred.

[0170] When using a film formed of plastic material as a support, examples of plastic materials include: polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"); acrylic polymers such as polycarbonate (hereinafter sometimes abbreviated as "PC"); polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA"); cyclic polyolefins; triacetyl cellulose (hereinafter sometimes abbreviated as "TAC"); polyether sulfides (hereinafter sometimes abbreviated as "PES"); polyether ketones; and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0171] When using metal foil as a support, examples of metal foils include copper foil and aluminum foil. Copper foil is preferred. Copper foil can be made from copper alone or from an alloy of copper with other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0172] For the support, the surface that bonds with the resin composition layer can be treated with matte finish, corona treatment, antistatic treatment, etc.

[0173] Furthermore, as a support, a support with a release layer can be used on the surface that bonds to the resin composition layer. As a release agent for the release layer of a support with a release layer, examples include one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. Commercially available release agents include, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, which are alkyd resin-based release agents. Furthermore, examples of supports with a release layer include, for example, "LUMIRROR T60" manufactured by Toray Industries, Ltd., "Purex" manufactured by Teijin Corporation, and "Unipeel" manufactured by Unitika Corporation.

[0174] The thickness of the support is preferably in the range of 5μm to 75μm, and more preferably in the range of 10μm to 60μm. It should be noted that when using a support with a release layer, it is preferable that the overall thickness of the support with the release layer is within the above range.

[0175] Resin sheets can be manufactured, for example, by applying a resin composition onto a support using a coating apparatus such as a die coater. Alternatively, if necessary, the resin composition can be dissolved in an organic solvent to prepare a resin varnish, which is then applied to manufacture the resin sheet. By using a solvent, the viscosity can be adjusted, improving coatability. When using a resin varnish, it is typically dried after coating to form a resin composition layer.

[0176] Drying can be carried out by known methods such as heating or hot air blowing. Regarding drying conditions, drying is generally carried out when the content of organic solvent in the resin composition layer is typically less than 10% by mass, preferably less than 5% by mass. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% to 60% by mass of organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0177] Resin sheets may include any layer other than the support and the resin composition layer, as needed. For example, in a resin sheet, a protective film selected according to the support may be provided on the side of the resin composition layer that is not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film helps to prevent dust and other contaminants from adhering to the surface of the resin composition layer or causing damage to the surface of the resin composition layer. When a resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. Furthermore, the resin sheet can be stored by rolling it into a roll.

[0178] Resin sheets are suitable for forming insulating layers in the manufacture of semiconductor chip packages (insulating resin sheets for semiconductor chip packages). For example, resin sheets can be used to form insulating layers on circuit boards (insulating resin sheets for circuit boards). Examples of packages using such substrates include FC-CSP, MIS-BGA packages, and ETS-BGA packages.

[0179] In addition, resin sheets can be suitable for sealing semiconductor chips (resin sheets for sealing semiconductor chips). Examples of suitable semiconductor chip packages include: Fan-out type WLP, Fan-in type WLP, Fan-out type PLP, Fan-in type PLP, etc.

[0180] In addition, resin sheets can be used as materials for MUFs (Mechanical Units) after semiconductor chips are connected to substrates.

[0181] Furthermore, resin sheets can be used in a wide range of other applications requiring high insulation reliability. For example, resin sheets can be suitably used to form the insulating layer of circuit boards such as printed wiring boards.

[0182] <Circuit Board>

[0183] The circuit board of the present invention comprises an insulating layer formed from a cured resin composition of the present invention. This circuit board can be manufactured, for example, by a manufacturing method including steps (1) and (2) described below.

[0184] (1) A process of forming a resin composition layer on a substrate;

[0185] (2) The process of heat curing the resin composition layer to form an insulating layer.

[0186] In step (1), a substrate is prepared. Examples of substrates include glass epoxy boards, metal substrates (stainless steel, cold-rolled steel sheet (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. Additionally, as part of the substrate, a metal layer such as copper foil may be present on its surface. For example, a substrate with a peelable first metal layer and a second metal layer on both surfaces may also be used. When using such a substrate, typically, a conductor layer that functions as a wiring layer for circuit wiring is formed on the side of the second metal layer opposite to the first metal layer. Examples of substrates with such a metal layer include Mitsui Metals & Minerals Co., Ltd.'s "Micro Thin" ultrathin copper foil with a carrier copper foil.

[0187] Additionally, a conductor layer may be formed on one or both surfaces of the substrate. In the following description, the component comprising the substrate and the conductor layer formed on the surface of the substrate is sometimes referred to as a "substrate with wiring layer". Examples of conductor materials included in the conductor layer include materials containing one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor material can be a single metal or an alloy. Examples of alloys include alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). From the viewpoints of versatility in conductor layer formation, cost, and ease of pattern formation, alloys of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals, and alloys of nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys are preferred. More preferably, single metals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, and nickel-chromium alloys; and particularly preferably single metals of copper.

[0188] For conductor layers, for example, to function as wiring layers, patterning can be applied. In this case, the linewidth (circuit width) / line spacing (width between circuits) ratio of the conductor layer is not particularly limited, but it is preferably 20 / 20 μm or less (i.e., a spacing of 40 μm or less), more preferably 10 / 10 μm or less, further preferably 5 / 5 μm or less, even more preferably 1 / 1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The spacing does not need to be uniform throughout the conductor layer. The minimum spacing of the conductor layer can be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

[0189] The thickness of the conductor layer depends on the design of the circuit board, preferably 3μm to 35μm, more preferably 5μm to 30μm, even more preferably 10μm to 20μm, and especially preferably 15μm to 20μm.

[0190] The conductor layer can be formed, for example, by a method including the following steps: laminating a dry film (photosensitive resist film) onto a substrate; exposing and developing the dry film under specified conditions using a photomask to form a pattern, thereby obtaining a patterned dry film; using the developed patterned dry film as a plating mask, forming the conductor layer using a plating method such as electroplating; and peeling off the patterned dry film. As the dry film, a photosensitive dry film formed from a photoresist composition can be used, for example, a dry film formed from resins such as phenolic varnish resin or acrylic resin. The lamination conditions of the substrate and the dry film can be the same as the lamination conditions of the substrate and resin sheet described later. The peeling off of the dry film can be carried out, for example, using an alkaline peeling solution such as sodium hydroxide solution.

[0191] After preparing the substrate, a resin composition layer is formed on the substrate. If a conductor layer is formed on the surface of the substrate, the formation of the resin composition layer is preferably performed by embedding the conductor layer within the resin composition layer.

[0192] The resin composition layer is formed, for example, by laminating a resin sheet to a substrate. This lamination can be performed, for example, by heating and pressing the resin sheet to the substrate from the support side, thereby bonding the resin composition layer to the substrate. Examples of components for heating and pressing the resin sheet to the substrate (hereinafter sometimes simply referred to as "heat-pressing component") include, for example, heated metal plates (SUS panels, etc.) or metal rollers (SUS rollers, etc.). It should be noted that, preferably, the heat-pressing component is not directly pressed onto the resin sheet, but rather the resin sheet is pressed through an elastic material such as heat-resistant rubber so that it fully conforms to the surface irregularities of the substrate.

[0193] The lamination of the substrate and the resin sheet can be performed, for example, using vacuum lamination. In vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C. The heating and pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa. The heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions below 13 hPa.

[0194] After lamination, the laminated resin sheet can be smoothed by pressing the heated bonding member from the support side under normal pressure (atmospheric pressure), for example. The pressing conditions for smoothing can be set to the same conditions as the heating and pressing conditions for lamination described above. It should be noted that lamination and smoothing can be performed continuously using a vacuum laminator.

[0195] Furthermore, the resin composition layer can be formed, for example, by compression molding. The molding conditions can be the same as those used in the process of forming the resin composition layer in the later-described step of forming the sealing layer of a semiconductor chip package.

[0196] After forming a resin composition layer on the substrate, the resin composition layer is thermocured to form an insulating layer. Although the thermocuring conditions of the resin composition layer vary depending on the type of resin composition, the curing temperature is generally in the range of 120°C to 240°C (preferably 150°C to 220°C, more preferably 170°C to 200°C), and the curing time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

[0197] The resin composition layer can be preheated at a temperature below the curing temperature before thermal curing. For example, the resin composition layer can be preheated for at least 5 minutes (preferably 5 to 150 minutes, more preferably 15 to 120 minutes) at a temperature of 50°C or higher and below 120°C (preferably 60°C or higher and below 110°C, more preferably 70°C or higher and below 100°C) before thermal curing.

[0198] By operating as described above, a circuit board with an insulating layer can be manufactured. Furthermore, the method for manufacturing the circuit board may include any steps. For example, when using a resin sheet to manufacture the circuit board, the method may include a step of peeling off a support from the resin sheet. The support may be peeled off before the resin composition layer is heat-cured, or it may be peeled off after the resin composition layer has been heat-cured.

[0199] The manufacturing method of the circuit board may include, for example, a step of grinding the surface of the insulating layer after its formation. There are no particular limitations on the grinding method. For example, a surface grinding wheel can be used to grind the surface of the insulating layer.

[0200] The manufacturing method of a circuit board may include, for example, a process of interlayer bonding of conductor layers (3) and a process of creating holes in the insulating layer. This allows through-holes, vias, and other holes to be formed in the insulating layer. Examples of methods for forming through-holes include laser irradiation, etching, and mechanical drilling. The size and shape of the through-holes can be appropriately determined according to the design of the circuit board. It should be noted that, for process (3), interlayer bonding can be achieved by grinding or polishing the insulating layer.

[0201] After forming the through-hole, it is preferable to perform a process to remove the smear material inside the through-hole. This process is sometimes referred to as the smear removal process. For example, when the conductor layer is formed on the insulating layer by a plating process, a wet smear removal process can be performed on the through-hole. Alternatively, when the conductor layer is formed on the insulating layer by a sputtering process, a dry smear removal process, such as a plasma treatment process, can be performed. Furthermore, the insulating layer can also be roughened by the smear removal process.

[0202] Alternatively, the insulating layer can be roughened before forming the conductor layer on the insulating layer. This roughening process typically roughens the surface of the insulating layer, including the interior of the through-hole. Both dry and wet roughening processes can be performed. Examples of dry roughening processes include plasma treatment. Examples of wet roughening processes include methods that sequentially perform expansion treatment using an expansion liquid, roughening treatment using an oxidizing agent, and neutralization treatment using a neutralizing liquid.

[0203] After forming the via, a conductor layer is formed on the insulating layer. By forming a conductor layer at the location where the via has been formed, the newly formed conductor layer becomes conductive with the conductor layer on the substrate surface, thus achieving interlayer bonding. Methods for forming the conductor layer include, for example, plating, sputtering, and vapor deposition, with plating being preferred. In a preferred embodiment, a suitable method such as a semi-additive or fully additive method is used to plating the surface of the insulating layer to form a conductor layer with the desired wiring pattern. Furthermore, when the support in the resin sheet is a metal foil, a subtractive method can be used to form a conductor layer with the desired wiring pattern. The material of the formed conductor layer can be a single metal or an alloy. Additionally, the conductor layer can have a single-layer structure or a multi-layer structure containing two or more layers of different types of materials.

[0204] Here, an example of an embodiment for forming a conductor layer on an insulating layer is described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, corresponding to the desired wiring pattern, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer. An electroplated layer is formed on the exposed plating seed layer by electroplating, and then the mask pattern is removed. Then, the unwanted plating seed layer is removed by etching or other processes, and a conductor layer having the desired wiring pattern can be formed. It should be noted that the dry film used in forming the mask pattern when forming the conductor layer is the same as the dry film described above.

[0205] The method for manufacturing a circuit board may include a step (4) of removing a substrate. By removing the substrate, a circuit board having an insulating layer and a conductor layer embedded in the insulating layer can be obtained. For example, this step (4) may be performed when a substrate having a peelable metal layer is used.

[0206] Semiconductor chip packaging

[0207] The first embodiment of the present invention relates to a semiconductor chip package comprising the circuit substrate described above and a semiconductor chip mounted on the circuit substrate. This semiconductor chip package can be manufactured by bonding the semiconductor chip to the circuit substrate.

[0208] Regarding the bonding conditions between the circuit board and the semiconductor chip, any condition that allows for conductive connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board can be used. For example, the conditions used in flip-chip mounting of semiconductor chips can be employed. Alternatively, for example, bonding between the semiconductor chip and the circuit board can be achieved via an insulating adhesive.

[0209] As an example of bonding methods, a method of pressing a semiconductor chip onto a circuit board can be cited. As for the pressing conditions, the pressing 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), and the pressing time is usually in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds).

[0210] Another example of a bonding method is bonding a semiconductor chip to a circuit board via reflow soldering. The reflow soldering conditions can be in the range of 120°C to 300°C.

[0211] After the semiconductor chip is bonded to the circuit board, it can be filled with a molding underfill material. The resin composition described above can be used as the molding underfill material, and the resin sheet described above can also be used.

[0212] The second embodiment of the present invention relates to a semiconductor chip package comprising a semiconductor chip and a cured form of the aforementioned resin composition sealing the semiconductor chip. In this type of semiconductor chip package, the cured form of the resin composition typically functions as a sealing layer. Examples of the semiconductor chip package according to the second embodiment include, for instance, a fan-out type WLP.

[0213] The manufacturing method of this type of semiconductor chip package includes the following steps:

[0214] (A) The process of laminating a temporary fixing film onto a substrate.

[0215] (B) The process of temporarily fixing the semiconductor chip onto the temporary fixing film.

[0216] (C) The process of forming a sealing layer on a semiconductor chip.

[0217] (D) The process of peeling the substrate and temporary fixing film from the semiconductor chip.

[0218] (E) A process of forming a rewiring layer as an insulating layer on the surface of a semiconductor chip where the substrate and temporary fixing film have been stripped.

[0219] (F) The process of forming a rewiring layer as a conductor layer on the rewiring forming layer, and,

[0220] (G) The process of forming a solder mask layer on the redistribution layer;

[0221] In addition, the aforementioned semiconductor chip packaging manufacturing method may include the following steps:

[0222] (H) The process of cutting multiple semiconductor chip packages into individual semiconductor chip packages for monolithic assembly.

[0223] <Process (A)>

[0224] Process (A) is the process of laminating a temporary fixing film onto a substrate. The lamination conditions of the substrate and the temporary fixing film are the same as those of the lamination conditions of the substrate and the resin sheet in the circuit board manufacturing method.

[0225] Examples of substrates include: silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates such as FR-4 substrates obtained by permeating epoxy resin into glass fibers and then performing thermosetting treatment; and substrates formed from bismaleimide triazine resins such as BT resin.

[0226] For temporary fixation films, any material that can be peeled off from the semiconductor chip and temporarily fixed to the semiconductor chip can be used. Commercially available examples include "REVALPHA" manufactured by Nitto Denko Corporation.

[0227] <Process (B)>

[0228] Process (B) is the process of temporarily fixing the semiconductor chip onto a temporary fixing film. Temporary fixing of the semiconductor chip can be performed using devices such as flip chip bonders or die bonders. The layout and number of semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production quantity of the target semiconductor chip package, etc. For example, the semiconductor chips can be arranged in a matrix with multiple rows and columns for temporary fixing.

[0229] <Process (C)>

[0230] Step (C) is the process of forming a sealing layer on a semiconductor chip. The sealing layer is formed from a cured product of the aforementioned resin composition. The sealing layer is typically formed by a method comprising the steps of: forming a resin composition layer on a semiconductor chip; and thermally curing the resin composition layer to form the sealing layer.

[0231] To effectively utilize the excellent compressibility of the resin composition, the formation of the resin composition layer is preferably carried out using a compression molding method. In a typical compression molding process, a semiconductor chip and a resin composition are placed in a mold, within which pressure is applied to the resin composition and, if necessary, heated to form a resin composition layer covering the semiconductor chip.

[0232] The compression molding process can be performed as follows: An upper mold (upper die) and a lower mold (lower die) are prepared as the molds for compression molding. A resin composition is then applied to the semiconductor chip, which is temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the resin composition, along with the substrate and the temporary fixing film, is mounted on the lower mold. Then, the upper and lower molds are closed, and heat and pressure are applied to the resin composition to perform compression molding.

[0233] Alternatively, the compression molding process can be performed as follows: An upper mold and a lower mold are prepared as the molds for compression molding. A resin composition is placed in the lower mold. A semiconductor chip, along with a substrate and a temporary fixing film, is then mounted in the upper mold. The upper and lower molds are then closed so that the resin composition placed in the lower mold is in contact with the semiconductor chip mounted in the upper mold, and heat and pressure are applied to perform compression molding.

[0234] Molding conditions vary depending on the composition of the resin composition, and appropriate conditions can be used to achieve good sealing. For example, the mold temperature during molding is preferably a temperature at which the resin composition exhibits excellent compressibility, preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 120°C or higher, preferably 200°C or lower, more preferably 170°C or lower, and particularly preferably 150°C or lower. Furthermore, the pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 5 minutes or more, preferably 60 minutes or lower, more preferably 30 minutes or lower, and particularly preferably 20 minutes or lower. Generally, the mold is removed after the resin composition layer is formed. Mold removal can be performed before or after heat curing of the resin composition layer.

[0235] The resin composition layer can be formed by stacking a resin sheet with a semiconductor chip. For example, the resin composition layer can be formed on the semiconductor chip by heating and pressing the resin composition layer of the resin sheet with the semiconductor chip. For the stacking of the resin sheet and the semiconductor chip, the semiconductor chip can usually be used instead of the substrate, and the process is carried out in the same way as the stacking of the resin sheet and the substrate in the manufacturing method of the circuit board.

[0236] After forming a resin composition layer on a semiconductor chip, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor chip. Thus, the semiconductor chip is sealed using the cured resin composition. The thermal curing conditions of the resin composition layer can be the same as those used in the method for manufacturing a circuit board. Furthermore, before thermally curing the resin composition layer, a preheating treatment can be performed on the resin composition layer at a temperature lower than the curing temperature. The preheating treatment conditions can be the same as those used in the preheating treatment method for manufacturing a circuit board.

[0237] <Process (D)>

[0238] Step (D) is the process of peeling the substrate and temporary fixing film from the semiconductor chip. The peeling method is preferably one appropriately selected based on the material of the temporary fixing film. Examples of peeling methods include heating the temporary fixing film to cause it to foam or expand, thereby peeling it off. Another example of a peeling method is irradiating the temporary fixing film with ultraviolet light through the substrate, thereby reducing the adhesive strength of the temporary fixing film and peeling it off.

[0239] In methods involving heating the temporary fixation film to cause it to foam or expand for peeling, the heating conditions are typically 100°C to 250°C for 1 to 90 seconds or 5 to 15 minutes. Alternatively, in methods involving irradiating the temporary fixation film with ultraviolet light to reduce its adhesive strength for peeling, the ultraviolet radiation dose is typically 10 mJ / cm². 2 ~1000mJ / cm 2 .

[0240] <Process (E)>

[0241] Process (E) is a process of forming a rewiring layer as an insulating layer on the surface of a semiconductor chip where the substrate and temporary fixing film have been stripped.

[0242] The material for the redistribution layer can be any insulating material. From the viewpoint of ease of semiconductor chip packaging manufacturing, photosensitive resins and thermosetting resins are preferred. Furthermore, the resin composition of the present invention can be used as the thermosetting resin.

[0243] After the redistribution layer is formed, vias can be formed on the redistribution layer to enable interlayer connections between the semiconductor chip and the redistribution layer.

[0244] In methods for forming through-holes when the redistribution layer is made of photosensitive resin, typically, active energy rays are irradiated onto the surface of the redistribution layer through a mask pattern, causing photocuring of the irradiated portion of the redistribution layer. Examples of active energy rays include ultraviolet light, visible light, electron beams, and X-rays, with ultraviolet light being particularly preferred. The amount and duration of ultraviolet irradiation can be appropriately set depending on the photosensitive resin. Examples of exposure methods include contact exposure, where the mask pattern is in close contact with (adhered to) the redistribution layer, and non-contact exposure, where the mask pattern is not in close contact with the redistribution layer and parallel light is used for exposure.

[0245] After photocuring the rewire formation layer, the rewire formation layer is developed to remove unexposed areas and form vias. For development, either wet or dry development can be used. Examples of development methods include immersion, puddle, spray, brush, and scraping; from a resolution perspective, puddle is preferred.

[0246] Methods for forming through-holes when the material for the redistribution layer is a thermosetting resin include, for example, laser irradiation, etching, and mechanical drilling. Among these, laser irradiation is preferred. Laser irradiation can be performed using a suitable laser processing machine that utilizes light sources such as carbon dioxide lasers, UV-YAG lasers, or excimer lasers.

[0247] There are no particular restrictions on the shape of the via, and it is generally acceptable to use a circle (approximately circular). The top diameter of the via is preferably less than 50 μm, more preferably less than 30 μm, further preferably less than 20 μm, preferably more than 3 μm, more preferably more than 10 μm, and even more preferably more than 15 μm. Here, the top diameter of the via refers to the opening diameter of the via at the surface of the redistribution layer.

[0248] <Process (F)>

[0249] Process (F) is the process of forming a rewiring layer as a conductor layer on the rewiring forming layer. The method of forming the rewiring layer on the rewiring forming layer can be the same as the method of forming a conductor layer on an insulating layer in the circuit board manufacturing process. Alternatively, processes (E) and (F) can be performed repeatedly to alternately deposit (stack) the rewiring layer and the rewiring forming layer.

[0250] <Process (G)>

[0251] Step (G) is the process of forming a solder resist layer on the redistribution layer. Regarding the material of the solder resist layer, any material with insulating properties can be used. From the viewpoint of ease of manufacturing semiconductor chip packages, photosensitive resins and thermosetting resins are preferred. Furthermore, the resin composition of the present invention can be used as the thermosetting resin.

[0252] Additionally, in process (G), bump forming can be performed as needed. Bump forming can be performed using methods such as solder balls or solder plating. Furthermore, the through-hole formation during bump forming can be performed in the same manner as in process (E).

[0253] <Process (H)>

[0254] In addition to processes (A) to (G), the manufacturing method for semiconductor chip packages may also include process (H). Process (H) is the process of cutting multiple semiconductor chip packages into individual semiconductor chip packages for monolithic fabrication. There are no particular restrictions on the method of cutting semiconductor chip packages into individual semiconductor chip packages.

[0255] Semiconductor Devices

[0256] Semiconductor devices are equipped with semiconductor chip packages. Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, smartphones, tablet computers, wearable devices, digital cameras, medical devices, and televisions) and vehicles (such as motorcycles, automobiles, trams, ships, and airplanes).

[0257] [Example]

[0258] The present invention will now be specifically described through examples. The present invention is not limited to these examples. It should be noted that, unless otherwise explicitly stated, in the following description, "parts" and "%" refer to "parts by mass" and "% by mass," respectively.

[0259] <Synthesis Example 1: Synthesis of Elastomers>

[0260] 368.41 g of diethylene glycol monoethyl ether acetate and 368.41 g of SOLVESSO 150 (registered trademark) (an aromatic solvent, manufactured by ExxonMobil) were added to a flask equipped with a stirrer, thermometer, and condenser. Then, 100.1 g (0.4 mol) of diphenylmethane diisocyanate and 400 g (0.2 mol) of polycarbonate diol (number average molecular weight: approximately 2000, hydroxyl equivalent: 1000, non-volatile components: 100%, manufactured by Kuraray Co., Ltd., "C-2015N") were added, and the reaction was carried out at 70°C for 4 hours. Next, 195.9 g (0.2 mol) of nonylphenol phenolic resin (hydroxyl equivalent 229.4 g / eq, average functionality 4.27, average calculated molecular weight 979.5 g / mol) and 41.0 g (0.1 mol) of 1,2-ethylene di[1,3-dihydro-1,3-dioxoisobenzofuran-5-carboxylic acid ester] (ethylene glycol bisanhydrotrimellitate) were added, and the mixture was heated to 150 °C for 12 hours. The reaction was carried out by FT-IR at 2250 cm⁻¹. -1 The disappearance of the NCO peak was confirmed. The reaction endpoint was considered reached when the NCO peak disappeared. The reactants were cooled to room temperature and then filtered through a 100-mesh filter cloth to obtain a resin with a polycarbonate structure (50% by mass of non-volatile components). The number average molecular weight of the obtained resin (elastomer) was 6100.

[0261] <Example 1>

[0262] Four parts of the elastomer (50% by mass of non-volatile components) synthesized in Synthesis Example 1, two parts of rubber particles (PARALOID EXL-2655 manufactured by Dow Chemical Company), three parts of naphthalene-type epoxy resin (ESN-475V manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent approximately 332 g / eq.), six parts of liquid epoxy resin (ZX1059 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent 169 g / eq.), 8.3 parts of a phenolic phenolic curing agent containing a triazine skeleton (LA-7054 manufactured by DIC Corporation, MEK solution with hydroxyl equivalent 125 and 60% non-volatile components), and silica A (average particle size 3 μm, specific surface area 4 m²) were used. 2125 parts of a resin varnish (surface treated with KBM573), 0.1 parts of a curing accelerator (2-phenyl-4-methylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd., "2P4MZ"), 10 parts of methyl ethyl ketone (MEK), and 8 parts of cyclohexanone were mixed and uniformly dispersed using a high-speed rotary mixer to prepare resin varnish 1.

[0263] <Example 2>

[0264] The following were prepared: 8 parts of the elastomer synthesized in Synthesis Example 1 (50% by mass of non-volatile components), 3 parts of naphthalene-type epoxy resin (NEC Steel & Sumitomo Chemical Co., Ltd. "ESN-475V", epoxy equivalent approximately 332 g / eq.), 6 parts of liquid epoxy resin (NEC Steel & Sumitomo Chemical Co., Ltd. "ZX1059", a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent 169 g / eq.), 8.3 parts of a phenolic phenolic curing agent containing a triazine skeleton (DIC Corporation "LA-7054", hydroxyl equivalent 125, MEK solution with 60% non-volatile components), and silica A (average particle size 3 μm, specific surface area 4 m²). 2 125 parts of resin varnish (surface treated with KBM573), 0.1 parts of curing accelerator (2-phenyl-4-methylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd., "2P4MZ"), 10 parts of methyl ethyl ketone (MEK), and 8 parts of cyclohexanone were mixed and dispersed evenly using a high-speed rotary mixer to prepare resin varnish 2.

[0265] <Example 3>

[0266] Four parts of the elastomer (50% by mass of non-volatile component) synthesized in Synthesis Example 1, six parts of liquid epoxy resin (Nippon Steel & Sumitomo Chemical Co., Ltd. "ZX1059", a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent 169 g / eq.), six parts of glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630", epoxy equivalent 90-105 g / eq.), seven parts of anhydride-based curing agent (Nippon Rikka Co., Ltd. "MH-700", 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70 / 30), and silica B (average particle size 9 μm, specific surface area 5 m²) were prepared. 2 140 parts of resin varnish (surface treated with KBM573), 0.1 parts of curing accelerator (methyl tritert-butylphosphonium dimethyl phosphate, manufactured by Nippon Chemical Industry Co., Ltd., "HISHICOLIN PX-4MP"), 10 parts of methyl ethyl ketone (MEK), and 8 parts of cyclohexanone were mixed and uniformly dispersed using a high-speed rotary mixer to prepare resin varnish 3.

[0267] <Comparative Example 1>

[0268] The following components were used in Synthesis Example 1: 14 parts of elastomer (50% by mass of non-volatile components), 2 parts of rubber particles (PARALOID EXL-2655 manufactured by Dow Chemical Company), 2 parts of naphthalene-type epoxy resin (ESN-475V manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent approximately 332 g / eq.), 4 parts of liquid epoxy resin (ZX1059 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent 169 g / eq.), 5 parts of phenolic phenolic curing agent containing a triazine skeleton (LA-7054 manufactured by DIC Corporation, MEK solution with 125 hydroxyl equivalent and 60% non-volatile components), and silica A (average particle size 3 μm, specific surface area 4 m²). 2 125 parts of a resin varnish (surface treated with KBM573), 0.1 parts of a curing accelerator (2-phenyl-4-methylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd., "2P4MZ"), 10 parts of methyl ethyl ketone (MEK), and 8 parts of cyclohexanone were mixed and dispersed evenly using a high-speed rotary mixer to prepare resin varnish 4.

[0269] <Comparative Example 2>

[0270] Four parts of the elastomer (50% by mass of non-volatile components) synthesized in Synthesis Example 1, two parts of rubber particles (PARALOID EXL-2655 manufactured by Dow Chemical Company), six parts of liquid epoxy resin (ZX1059 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (by mass ratio), epoxy equivalent 169 g / eq.), three parts of polyalkylene oxide resin (EXA-4816 manufactured by DIC Corporation, epoxy equivalent 403 g / eq.), a phenolic phenolic curing agent containing a triazine skeleton (LA-7054 manufactured by DIC Corporation, MEK solution with hydroxyl equivalent 125 and 60% non-volatile components), and silica A (average particle size 3 μm, specific surface area 4 m²) were used. 2 125 parts of a resin varnish (surface treated with KBM573), 0.1 parts of a curing accelerator (2-phenyl-4-methylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd., "2P4MZ"), 10 parts of methyl ethyl ketone (MEK), and 8 parts of cyclohexanone were mixed and dispersed evenly using a high-speed rotary mixer to prepare resin varnish 5.

[0271] <Comparative Example 3>

[0272] Two parts of naphthalene-type epoxy resin (NEC Steel & Sumitomo Chemical Co., Ltd. "ESN-475V", epoxy equivalent approximately 332 g / eq.), seven parts of liquid epoxy resin (Nippon Soda Co., Ltd. "JP-100", epoxy equivalent 190-210 g / eq.), eight parts of liquid epoxy resin (NEC Steel & Sumitomo Chemical Co., Ltd. "ZX1059", a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent 169 g / eq.), five parts of a phenolic phenolic curing agent containing a triazine skeleton (DIC Co., Ltd. "LA-7054", hydroxyl equivalent 125, MEK solution with 60% non-volatile components), and silica A (average particle size 3 μm, specific surface area 4 m²). 2 125 parts of a resin varnish (surface treated with KBM573), 0.1 parts of a curing accelerator (2-phenyl-4-methylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd., "2P4MZ"), 10 parts of methyl ethyl ketone (MEK), and 8 parts of cyclohexanone were mixed and dispersed evenly using a high-speed rotary mixer to prepare resin varnish 6.

[0273] <Experimental Example 1: Oxygen Permeability>

[0274] For the resin varnishes manufactured in the various embodiments and comparative examples, a cured sheet A or B is prepared for measuring the oxygen permeability by a process of forming a resin composition layer and a process of heat curing the resin composition layer at 180°C for 90 minutes. The details are as follows.

[0275] (Preparation of resin sheet A)

[0276] As a support, a PET film (Toray Industries Ltd.'s "LUMIRRORR80", thickness 38μm, softening point 130℃, "release PET") that has been demolded with an alkyd resin-based release agent (Lintec Corporation's "AL-5") is prepared.

[0277] Using a die coater, resin varnishes 1, 2, and 4-6 prepared in Examples 1 and 2, and Comparative Examples 1-3, were uniformly coated onto the release PET to achieve a resin composition layer thickness of 150 μm after drying. The coated layers were then dried at 70°C to 95°C for 2 minutes, resulting in a sheet with a resin composition layer on the release PET. Next, on the surface of the sheet not bonded to the support, a rough surface of a polypropylene film (Oji F-Tex "ALPHAN MA-411", 15 μm thick) serving as a protective film was laminated to the resin composition layer. This yielded five types of resin sheets A, sequentially comprising a release PET (support), a resin composition layer, and a protective film.

[0278] (Preparation of Cured Sheet A)

[0279] Protective films were peeled off from five different resin sheets A. Two sheets A were then laminated together using an intermittent vacuum pressure laminator (Nikko-Materials, 2-stage stacking laminator, CVP700) with the resin composition layers joined together. The lamination was performed as follows: a 30-second depressurization was applied, the pressure was adjusted to below 13 hPa, and then a 45-second pressing was performed at 130°C and 0.74 MPa. Then, one side of the release PET was peeled off, and the resin composition layer was cured at 180°C for 90 minutes. The other side of the release PET was then peeled off, producing five types of cured sheets A.

[0280] (Preparation of Cured Sheet B)

[0281] Using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, curing time: 10 minutes), the resin varnish 3 manufactured in Example 3 was compressed onto an SUS board whose surface had undergone a release treatment to form a resin composition layer with a thickness of 300 μm. The SUS board was then peeled off, and the resin composition layer was thermocured by heating at 180°C for 90 minutes to obtain a cured sheet B of the resin composition.

[0282] (Determination of oxygen permeability and calculation of oxygen permeability coefficient)

[0283] Using an oxygen permeability measuring apparatus (MOCON, OX-TRAN2 / 21), the oxygen permeability of five types of cured sheet A and cured sheet B was measured according to JIS-K7126 (isobaric method) at 23°C and 0% RH. It should be noted that RH represents relative humidity. Furthermore, for each of the five types of cured sheet A and cured sheet B, the oxygen permeability coefficient (cc / (atm·m)) was calculated by dividing the obtained oxygen permeability by the thickness. 2 (day / mm). The results are shown in Table 1 below.

[0284] <Experimental Example 2: Coefficient of Linear Thermal Expansion (CTE)>

[0285] For the resin varnishes manufactured in the various embodiments and comparative examples, a cured product A or B for measuring the coefficient of linear thermal expansion is prepared by a process of forming a resin composition layer and a process of thermally curing the resin composition layer by heating at 180°C for 90 minutes. The details are as follows.

[0286] (Evaluation of the preparation of cured product A)

[0287] Using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, curing time: 10 minutes), the resin varnish 3 manufactured in Example 3 was compressed onto an SUS board whose surface had undergone a release treatment to form a resin composition layer with a thickness of 300 μm. The SUS board was then peeled off, and the resin composition layer was thermocured by heating at 180°C for 90 minutes to obtain cured resin composition A for evaluation.

[0288] (Preparation of resin sheet B)

[0289] On the untreated side of the PET film (Lintec Corporation "501010", 38μm thick, 240mm square) treated with release agent, a double-sided copper-clad epoxy resin laminate (Panasonic Corporation "R5715ES", 0.7mm thick, 255mm square) is overlapped with a glass cloth substrate and fixed with polyimide tape (10mm wide) (hereinafter sometimes referred to as "fixing the PET film").

[0290] Using a die coater, resin varnishes 1, 2 and 4-6 prepared in Examples 1 and 2 and Comparative Examples 1-3 were coated onto the demolding surface of the above-mentioned "fixed PET film" to make the thickness of the dried resin composition layer 100 μm. The film was dried at 80°C to 120°C (average 100°C) for 10 minutes to obtain 5 kinds of resin sheets B.

[0291] (Evaluation of the preparation of cured product B)

[0292] Five types of resin sheets B were placed in an oven at 180°C and then heat-cured for 90 minutes to form a resin composition layer.

[0293] After heat curing, the polyimide tape is peeled off, and the cured product is removed from the glass cloth substrate epoxy resin double-sided copper-clad laminate. Then, the PET film (Lintec Corporation "501010") is also peeled off to obtain 5 kinds of sheet-like evaluation cured products B.

[0294] (Determination of linear thermal expansion coefficient)

[0295] Evaluation cured material A and five evaluation cured materials B were cut into specimens 5 mm wide and 15 mm long. These specimens were then subjected to thermomechanical analysis using a Rigaku Thermo Plus TMA8310 apparatus via the tensile loading method. Specifically, the specimens were mounted on the apparatus and measured twice consecutively under conditions of a 1 g load and a heating rate of 5 °C / min. In the second measurement, the linear thermal expansion coefficient (ppm / °C) in the planar direction within the range of 25 °C to 150 °C was calculated. The results are shown in Table 1 below.

[0296] <Experimental Example 3: Warpage Evaluation>

[0297] For the resin varnishes manufactured in the various embodiments and comparative examples, a sample substrate A or B for evaluating warpage is prepared by a process of forming a resin composition layer on a silicon wafer and a process of thermally curing the resin composition layer by heating at 180°C for 90 minutes. The details are as follows.

[0298] (Fabrication of sample substrate A)

[0299] Using an intermittent vacuum pressure laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.), the five types of resin sheets A prepared in Test Example 1 were laminated onto a 12-inch silicon wafer (775 μm thick) with the first main surface of the resin composition layer bonded to it. The lamination was performed as follows: a 30-second decompression was applied to bring the pressure down to below 13 hPa, followed by a 30-second pressing at 100°C and 0.74 MPa. Two laminations were performed to form a resin composition layer with a thickness of 300 μm. Then, the resin composition layer was thermocured at 180°C for 90 minutes. This yielded five sample substrates A comprising a silicon wafer and a cured resin composition layer.

[0300] (Fabrication of sample substrate B)

[0301] Regarding Example 3, resin varnish 3 was compressed onto a 12-inch silicon wafer (775 μm thick) using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, curing time: 10 minutes). The resin composition layer was then thermocured at 180°C for 90 minutes. This yielded sample substrate B, a cured product comprising a silicon wafer and a 300 μm resin composition layer.

[0302] (Warpage Assessment)

[0303] Five sample substrates, A and B, were heated and cooled sequentially at 35°C, 260°C, and 35°C, respectively. The resulting warpage was measured using a shadow moire measuring device (Akorometrix Thermoire AXP). The measurements were performed according to JEITA EDX-7311-24 standard. Specifically, the fitted plane obtained using the least squares method for all data on the sample substrate surface in the measurement area was used as the reference plane. The difference between the minimum and maximum values ​​perpendicular to this reference plane was taken as the warpage. Warpage less than 2 mm was marked "○", and warpage greater than 2 mm was marked "×", thus evaluating "warpage".

[0304] <Experimental Example 4: Elongation Evaluation>

[0305] For the resin varnishes manufactured in the various embodiments and comparative examples, test pieces A or B for evaluating elongation are prepared by a process of forming a resin composition layer, a process of heat-curing the resin composition layer at 180°C for 90 minutes, and a process of cutting out the cured layer obtained by heat curing. The details are as follows.

[0306] (Production of Test Film A)

[0307] Using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, curing time: 10 minutes), the resin varnish 3 manufactured in Example 3 was compressed onto an SUS board with a surface that had undergone a release treatment, forming a resin composition layer with a thickness of 100 μm. The SUS board was peeled off, and the resin composition layer was thermo-cured by heating at 180°C for 90 minutes or 180°C for 24 hours in atmospheric conditions, resulting in a cured layer of the resin composition. This cured layer was cut into dumbbell-shaped No. 1 pieces, yielding two types of specimens A for one resin composition (curing conditions: 90 minutes at 180°C and 24 hours at 180°C).

[0308] (Production of Test Film B)

[0309] The resin sheet B obtained in Example 2 was placed in an oven at 180°C and the resin composition layer was heat-cured under curing conditions of 90 minutes or 24 hours.

[0310] After heat curing, the polyimide tape was peeled off, and the cured material was removed from the glass cloth substrate epoxy resin double-sided copper-clad laminate. Then, the PET film (Lintec "501010") was also peeled off, resulting in a sheet-like cured material. The obtained cured material was cut into dumbbell-shaped No. 1 pieces, yielding two types of test pieces B for one type of resin sheet B (curing conditions: 90 minutes at 180°C and 24 hours at 180°C).

[0311] (Elongation evaluation)

[0312] Two samples, A and B, were tested for elongation at 23°C using an Orientec RTC-1250A tensile testing machine (curing conditions: 90 minutes and 24 hours at 180°C). The elongation was determined according to JIS K7127. The test was performed three times, and the average elongation (%) was calculated.

[0313] Furthermore, the elongation after curing at 180°C for 24 hours was calculated from the obtained elongation value, relative to the elongation after curing at 180°C for 90 minutes. A ratio below 0.70 was marked "×", and a ratio above 0.70 was marked "〇", thus evaluating "brittleness". A higher elongation ratio indicates more suppressed embrittlement. The results are shown in Table 1 below.

[0314] [Table 1]

[0315]

[0316] The results above show that the desired effect of the present invention can be obtained if the following resin composition is used; the resin composition is a resin composition containing (A) epoxy resin and (B) curing agent, wherein the oxygen permeability coefficient of the cured product obtained by heat curing the resin composition at 180°C for 90 minutes is 3cc / (atm·m). 2 For temperatures below 1000 mm, the linear thermal expansion coefficient of the cured material is 4–15 ppm / ℃.

Claims

1. A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) an elastomer, wherein the (A) epoxy resin does not include component (D). in, (A) The composition contains liquid epoxy resin, and when the resin component in the resin composition is set to 100% by mass, the content of liquid epoxy resin is 20-70% by mass. (C) is composed only of silicon dioxide. When the non-volatile component in the resin composition is set at 100% by mass, the content of component (C) is 70% by mass or more. When the resin component in the resin composition is set to 100% by mass, the content of component (D) is 2-25% by mass. The resin component in a resin composition refers to the non-volatile components that constitute the resin composition, excluding (C) inorganic fillers.

2. The resin composition according to claim 1, wherein, (C) The average particle size of the component is greater than 2.5 μm.

3. The resin composition according to claim 1, wherein, (A) contains solid epoxy resin.

4. The resin composition according to claim 1, wherein, When the resin component in the resin composition is set to 100% by mass, the content of component (A) is 40% by mass or more.

5. The resin composition according to claim 1, wherein, The epoxy equivalent of the epoxy resin contained as component (A) is 400 g / eq. or less.

6. The resin composition according to claim 1, wherein, (B) The ingredients contain phenolic curing agents or acid anhydride curing agents.

7. The resin composition according to claim 1, wherein, (D) Component contains polycarbonate resin.

8. The resin composition according to claim 1, wherein, The oxygen permeability coefficient of the cured product obtained by heat curing the resin composition at 180°C for 90 minutes is 3 cc / (atm·m). 2 (day / mm) and below.

9. The resin composition according to claim 8, wherein, The coefficient of linear thermal expansion of the cured product obtained by heat curing the resin composition at 180°C for 90 minutes is 4 to 15 ppm / °C.

10. The resin composition according to claim 1, wherein, The ratio of the elongation at 23°C of the cured product obtained by heat curing the resin composition at 180°C for 24 hours to the elongation at 23°C of the cured product obtained by heat curing the resin composition at 180°C for 90 minutes to the elongation at 23°C as determined by JIS K7127 is 0.7 or more.

11. The resin composition according to claim 1, wherein, This resin composition is used to seal semiconductor chips in semiconductor chip packages.

12. A resin ink, wherein, A resin composition comprising any one of claims 1 to 11.

13. A resin ink layer formed from the resin ink of claim 12 and having a thickness of 100 μm or more.

14. A resin sheet, wherein, have: Support body, and A resin composition layer comprising the resin composition according to any one of claims 1 to 11 is disposed on the support.

15. The resin sheet according to claim 14, wherein, The thickness of the resin composition layer is 100 μm or more.

16. A semiconductor chip packaging article, wherein, A cured product comprising the resin composition according to any one of claims 1 to 11.

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