JP5471423B2 - Underfill agent and semiconductor device using the same - Google Patents

Description

  The present invention relates to an underfill agent. More specifically, the present invention relates to an underfill agent that is preferably used for bonding a semiconductor element and a substrate.

  In recent years, the increase in size of semiconductor elements has rapidly progressed, and a large thermal stress has been generated between the semiconductor elements and the substrate. 2. Description of the Related Art Conventionally, a technique is known in which, after bonding between a semiconductor element and a substrate, a gap is filled with an epoxy-based underfill agent to disperse stress and thereby increase bonding reliability at the semiconductor element / substrate interface. The characteristics required for the underfill agent are that it quickly enters the gap between the semiconductor element and the substrate, does not cause voids, has good storage stability, and is connected to thermal and physical stress after curing. High reliability, heat resistance and toughness, short time and low temperature curability. Since epoxy resins are hard and brittle, techniques for mixing various thermoplastic resins with epoxy resins have been proposed in order to absorb more mechanical and thermal stresses. For example, a thermosetting resin composition containing a bismaleimide compound and an epoxy resin (for example, see Patent Document 1), or a liquid epoxy resin composition containing a liquid epoxy resin, a curing agent, and a polyether compound (for example, a patent) Reference 2) is disclosed. However, the resin compositions disclosed therein have a problem that the storage stability is insufficient, such as high viscosity and gelation over time. On the other hand, as a thermosetting resin composition having excellent heat resistance, a resin composition containing an epoxy resin, a polyhydric phenol epoxy resin curing agent and polyethersulfone has been proposed (see, for example, Patent Document 3). ). In addition, an underfill agent containing a polyimide resin, an epoxy resin, and a high-boiling solvent and having a solution viscosity at 25 ° C. of 500 centipoise or less has been proposed (for example, see Patent Document 4). These materials are dissolved in a high boiling point solvent such as triglyme, and when this is used as an underfill agent, voids are generated due to scattering of the high boiling point solvent after bonding, and the reliability decreases. It was not practical, such as increasing the viscosity.

JP 2003-221443 A (Claims) JP 2008-81686A (Claims) JP 2001-72833 A (Claims) JP 2000-154250 A (Claims)

  Thus, in the prior art, an underfill agent having both storage stability and viscosity characteristics has not been obtained. In order to solve the above problems, an object of the present invention is to provide an underfill agent excellent in storage stability and viscosity characteristics.

The present invention, (a) containing a weight average molecular weight of 30,000 or more polyether sulfone resin, a (b) an epoxy compound state, and are 1 wt% or less content of (c) a solvent, (b) an epoxy compound Is an aliphatic glycidyl ether type epoxy compound having an SP value of 1.60 × 10 ^{4 to} 1.80 × 10 ⁴ (J / m ³ ) ^1/2 , and an SP value of 2.00 × 10 ⁴ to 2. It is an underfill agent characterized by containing at least one epoxy compound that is 60 × 10 ⁴ (J / m ³ ) ^1/2 .

  According to the present invention, an underfill agent having excellent storage stability and viscosity characteristics can be obtained.

DSC curve of the underfill agent of Example 7

Underfill agent of the present invention and (a) a weight-average molecular weight of 30,000 or more polyether sulfone resin, (b) containing epoxy compound state, and are 1 wt% or less content of (c) a solvent, (b ) An aliphatic glycidyl ether type epoxy compound having an SP value of 1.60 × 10 ^{4 to} 1.80 × 10 ⁴ (J / m ³ ) ^1/2 and an SP value of 2.00 × 10 ⁴ It is characterized by containing 1 or more types of epoxy compounds which are -2.60x10 < ⁴ > (J / m < ³ > ) < ^1/2 > . Since it is substantially solvent-free, generation of voids can be suppressed and insulation reliability after bonding can be improved. The polyethersulfone resin has a rigid structure, has a very high glass transition temperature of 200 ° C. or higher, and is excellent in fluidity at high temperatures. By containing a polyether sulfone resin having a high glass transition temperature, the heat resistance (glass transition temperature) after curing of the resulting underfill agent can be improved. Furthermore, (a) a polyethersulfone resin having a weight average molecular weight of 30,000 or more is incompatible with (b) an epoxy compound under the conditions of 25 ° C. and 1.013 × 10 ⁵ N / m ² . For this reason, the polyethersulfone resin does not dissolve in the epoxy compound in the absence of a solvent, but is dispersed in the epoxy compound as particles. By having such a dispersed state, the polyethersulfone resin and the epoxy compound flow without agglomerating with each other, and thus have low viscosity characteristics. Therefore, the underfill agent of this invention is excellent in the applicability | paintability and permeability | transmittance to a board | substrate. Further, since the polyethersulfone resin is dispersed in the epoxy compound, the cohesive density in the system is low, so that the increase in viscosity and gelation with time can be suppressed, and the storage stability is excellent.

  Also, by heating the underfill agent of the present invention, the polyethersulfone resin particles dispersed in the epoxy compound are dissolved in the epoxy compound, and then undergo a curing reaction. Therefore, it can be used as a thermosetting reactive underfill agent that is uniformly dissolved by heat treatment while keeping excellent stability at low viscosity during storage.

  In the underfill agent of the present invention, it is important that the polyethersulfone resin (a) component has a weight average molecular weight of 30,000 or more in order to disperse in a particulate form without being dissolved with the (b) epoxy compound. is there. When the weight average molecular weight is less than 30,000, the viscosity of the resulting underfill agent is increased by dissolving in (b) the epoxy compound. Further, since the aggregation density increases, the storage stability is lowered due to increase in viscosity and gelation with time. In addition, the toughness after curing may be reduced. From the viewpoint of toughness after curing, the weight average molecular weight of the polyethersulfone resin (a) is preferably 40,000 or more, and more preferably 50,000 or more. On the other hand, 100,000 or less is preferable and 80,000 or less is more preferable in order to adjust the viscosity characteristics to a more appropriate range and further improve the permeability. Two or more kinds of polyethersulfone resins may be contained, and it is preferable that the weight average molecular weight of each resin is 30,000 or more.

The weight average molecular weight in the present invention is calculated by measuring the molecular weight of the polyethersulfone resin by a gel permeation chromatography (GPC) method using a mixed solvent of NMP / H ₃ PO ₄ and using a calibration curve of standard polystyrene. Indicates the value.

  The polyethersulfone resin can be obtained by reacting a phenolic hydroxyl group with an alkali metal carbonate to produce an alkali metal salt of a phenol compound, and reacting this with a dihalogenodiphenylsulfone. For example, an alkali metal salt of a phenol compound is synthesized in a reaction system, or an alkali metal salt of a phenol compound is synthesized in advance and reacted with dihalogenodiphenylsulfone in an organic solvent, and then terminated with dichloromethane. Techniques for performing the reaction are known. For example, in JP-A-53-12991 and JP-A-53-16098, 4,4′-hydroxydiphenylsulfone, 4,4′-dichlorodiphenylsulfone, and anhydrous potassium carbonate are used. A technique for producing polyethersulfone and blowing chloromethane after completion of the reaction is disclosed.

  Examples of the dihalogenodiphenylsulfone used in the polyethersulfone resin used in the present invention include 4,4′-dichlorodiphenylsulfone, 4,4′-difluorodiphenylsulfone, and 4-chloro-4′-fluorodiphenyl. Sulfone, 4,4′-dibromodiphenylsulfone, 1,4-bis (4-chlorobenzenesulfonyl) benzene, bis (4′-chlorobenzenesulfonyl) ether, 1,3-bis (4′-chlorobenzenesulfonyl) benzene, bis ( 3'-chlorobenzenesulfonyl) ether, 1,2-bis (4'-chlorobenzenesulfonyl) benzene, bis (2'-chlorobenzenesulfonyl) ether, 4,4'-bis (4-chlorophenylsulfonyl) diphenyl, and the like.

  Examples of the phenol compound used in the polyethersulfone resin used in the present invention include 4,4′-dihydroxydiphenylsulfone, 2,2′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl sulfide, and 4,4 ′. -Dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 4,4,4'-trihydroxytriphenylmethane, 2,2 ', 4,4'-tetrahydroxybenzophenone, 9,9'-bis (4-hydroxyphenyl) ) Fluorene, α, α, α-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, α, α′-bis (4-hydroxy-3,5-dimethylphenyl) -1,4-diisopropyl Benzene, 2,2′-bis (4′-hydroxyphenyl) propane, 2 , 2-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) propane, bis (4′-dihydroxyphenyl) propane, bis (4′-hydroxyphenyl) methane, bis (4′-hydroxyphenyl) cyclohexane 1,1-bis (4′-hydroxyphenyl) ethane, 1,4-bis (4′-hydroxyphenoxy) benzene, 1,3-bis (4′-hydroxyphenoxy) benzene, 1,4-bis (4 Divalent phenolic compounds such as' -hydroxybenzoyl) benzene, 1,3-bis (4'-hydroxybenzenesulfonyl) benzene, phenol, o-cresol, m-cresol, p-cresol, 2-aminophenol, 3 -Aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophene 4-aminothiophenol, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-ethoxyphenol, m- Ethoxyphenol, p-ethoxyphenol, on-propylphenol, o-isopropylphenol, mn-propylphenol, m-isopropylphenol, pn-propylphenol, p-isopropylphenol, on-butylphenol, o-sec- Tylphenol, o-tert-butylphenol, mn-butylphenol, m-sec-butylphenol, m-tert-butylphenol, pn-butylphenol, p-sec-butylphenol, p-tert-butylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2,4,6-trimethylphenol, o-benzylphenol, m-benzylphenol, p-benzyl Phenol, o-butoxyphenol, m-butoxyphenol, p-butoxyphenol, 6-tert-butyl-p-xylenol, 2-tert-butyl-p-xylenol, 2-tert-butyl-p-cresol, o-si Cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, 2,6-di-tert-butyl-p-cresol, 4,6-di-tert-butyl-4-hydroxymethylphenol, 2,4-dimethoxyphenol , Monovalent phenol compounds such as 2,6-dimethoxyphenol, vanillin, cumylphenol, and the like.

  In order to increase the weight average molecular weight of the polyethersulfone resin to 30,000 or more, 0.9 to 1.0 equivalent of dihalogenodiphenylsulfone with respect to the dihydric phenol compound and 0.45 to 1.55 with respect to the monovalent phenol compound. It is preferable to use 0.5 equivalent.

  Examples of the alkali metal of the alkali metal salt used in the polyethersulfone resin used in the present invention include lithium, sodium, potassium, and rubidium, and potassium or sodium is preferable. Examples of the metal compound used for forming the dialkali salt include hydroxides, carbonates, and hydrogen carbonates, and hydroxides or carbonates are preferable. Accordingly, potassium hydroxide, sodium hydroxide, potassium carbonate or sodium carbonate is preferable for forming a dialkali salt of bisphenols, and two or more of these may be used. The amount of these alkali metal salts varies depending on the type, but it is preferably at least 1 mol, more preferably at least 2 mol based on the bisphenol compound. If it is this range, the alkali metal salt of bisphenol can fully be produced | generated, and a high molecular weight polymer with a weight average molecular weight of 30,000 or more can be obtained easily. On the other hand, from the viewpoint of suppressing side reactions, it is preferably 8 times mol or less, more preferably 4 times mol or less.

  The polymerization temperature is preferably in the range of 100 to 300 ° C. By setting the temperature to 100 ° C. or higher, a high molecular weight polymer having a weight average molecular weight of 30,000 or more can be easily obtained. Moreover, the side reaction of a polymer can be suppressed by setting it as 300 degrees C or less. The polymerization time is preferably about 2 to 4 hours.

  The organic solvent used as the reaction solvent is preferably an aprotic polar solvent. For example, diphenyl sulfone, dimethyl sulfoxide, sulfolane, dimethyl sulfone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, diethyl sulfone, diethyl sulfoxide, 1,4-dimethylbenzazolidinone, Examples include hexamethyltriamide and 1,3-dimethylimidazolidinone. In addition, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl isobutyl ketone and cyclohexanone, ester solvents such as propylene glycol monomethyl ether acetate and methyl-methoxybutanol acetate can be added to these.

  The amount of the solvent used in the polycondensation is preferably 0.5 times or more, more preferably 2 times or more based on the weight of all monomers. By setting the amount of the solvent to 0.5 times or more with respect to the weight of all monomers, operations such as stirring are facilitated, and the polycondensation reaction easily proceeds smoothly. On the other hand, 20 times or less is preferable and 8 times or less is more preferable. By setting it to 20 times or less, the monomer concentration in the solvent is increased and the polymerization rate is improved, so that a high molecular weight polymer having a weight average molecular weight of 30,000 or more can be easily obtained.

  The polyethersulfone resin having a weight average molecular weight of 30,000 or more can be polymerized by a known technique as described above, but a general-purpose grade of a commercially available polyethersulfone resin may be used. Furthermore, it can superpose | polymerize and manufacture by making a phenolic compound and a metal salt react with a commercially available polyethersulfone resin in an organic solvent.

  As a commercially available product of the polyethersulfone resin, “Sumika Excel (registered trademark)” 3600P (weight average molecular weight 46100), “Sumika Excel” 4100P (weight average molecular weight 53250), “Sumika Excel” 4800P (weight average molecular weight 66700), “Sumika Excel” 5200P (weight average molecular weight 69700), “Sumika Excel” 5003P (weight average molecular weight 67250) (the trade name, manufactured by Sumitomo Chemical Co., Ltd.), “Ultrazon (registered trademark)” E2010 (weight average molecular weight) 55400), “Ultrazon” E2020P (weight average molecular weight 56700), “Ultrazon” E3010 (weight average molecular weight 62000), “Ultrazon” E6020P (weight average molecular weight 76000), (above, trade name, BASF JA "GAFONE (registered trademark)" 3000RP (weight average molecular weight 62000-64000), "GAFONE" 3100RP (weight average molecular weight 52000-53000), "GAFONE" 3200RP (weight average molecular weight 45000-47000), “GAFONE” 3600RP (weight average molecular weight 43000) (above, trade name, manufactured by Solvay Advanced Polymers Co., Ltd.). You may contain 2 or more types of these polyether sulfone resins.

  In the present invention, the content of the component (a) polyethersulfone resin is preferably 5% by weight or more, and more preferably 10% by weight or more. By setting the content to 5% by weight or more, the brittleness and hardness inherent in the epoxy resin can be improved. On the other hand, from the viewpoint of further reducing the viscosity and improving the permeability, the content is preferably 40% by weight or less, and more preferably 30% by weight or less.

  In the present invention, the polyethersulfone resin as component (a) may have a phenolic hydroxyl group, a fluoro group, a chloro group, a bromo group, a methoxy group, an ethoxy group, or the like at the terminal. You may have more. Among these, it is desirable to have a phenolic hydroxyl group. Having a phenolic hydroxyl group reacts with the oxirane ring of the epoxy compound or the reactive group of the epoxy compound to form a dense network structure, so that the resulting cured product exhibits high heat resistance and toughness.

The amount of the terminal phenolic hydroxyl group can be measured by determining the integrated value of the peak deposited from the nuclear magnetic resonance ( ¹ H-NMR) method. In the amount of the terminal functional group excluding the repeating unit in the resin, the phenolic hydroxyl group is preferably contained in an amount of 5 mol% or more, more preferably 30 mol% or more. By having 5 mol% or more of the phenolic hydroxyl group, the affinity with the epoxy compound is improved, and the heat resistance and toughness after curing are improved. On the other hand, 90 mol% or less is preferable and 80 mol% or less is more preferable. By setting it to 90 mol% or less, it is dispersed in the epoxy compound at room temperature, and the storage stability becomes better.

  Examples of the polyethersulfone resin having a phenol group at the terminal include “SUMICA EXCEL” 5003P, “Ultrazon” E2020P, “GAFONE” 3000RP, 3600RP, and the like.

  The polyethersulfone resin is preferably flaky or powdery, and more preferably powdery. The powdery polyethersulfone resin can be easily obtained by freeze-pulverizing a pellet-like or flake-like resin. The particle size of the powdered polyethersulfone resin is preferably 1 μm or more, and more preferably 5 μm or more. By setting the particle diameter to 1 μm or more, aggregation of particles can be suppressed and the particles can be more uniformly dispersed. On the other hand, 100 μm or less is preferable, and 30 μm or less is more preferable. By setting it to 100 μm or less, separation of the polyethersulfone resin particles having a low specific gravity and the epoxy compound can be suppressed, and the particles can be more uniformly dispersed.

  The underfill agent of the present invention contains (b) an epoxy compound. Epoxy resins have good thermal reactivity with other compounds, have high adhesive strength after curing, and can give molded products with little heat shrinkage.

  One preferred embodiment of the (b) epoxy compound in the present invention includes a glycidylamine type epoxy compound having a nitrogen atom in the molecule. Such an epoxy compound can shorten the curing reaction by the action of an intramolecular nitrogen atom. A glycidylamine type epoxy compound is synthesized by reacting an active hydrogen of a primary or secondary amine compound with epichlorohydrin to replace a glycidyl group. Among these, it is preferable to contain an epoxy compound represented by any one of the following general formulas (1) to (3). Since these aromatic glycidylamine type epoxy compounds have a high glass transition temperature after curing, the heat resistance of the cured product can be increased. Two or more of these may be contained.

In the general formulas (1) to (3), R ^{1 to} R ¹⁷ represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a fluoroalkyl group, or an aryl group, which may be the same or different. Also good. The alkyl group may be linear or cyclic. In the general formula (3), X ¹ represents a direct bond, an ether group, a thioether group, an SO ₂ group, an isopropylene group, or a group represented by the following general formula (4) or (5).

In the general formulas (4) to (5), R ^{18 to} R ²³ represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a fluoroalkyl group, or an aryl group. Also good. The alkyl group may be linear or cyclic. In the above general formula, X ² and X ³ represent a direct bond, an ether group, a thioether group, an SO ₂ group, an isopropylene group, or a group represented by the following general formula (6).

In the general formula (6), R ^{24 to} R ²⁵ represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a fluoroalkyl group, or an aryl group, and may be the same or different. The alkyl group may be linear or cyclic.

  Specific examples of the bifunctional glycidylamine represented by the general formula (1) include diglycidylaniline, diglycidyltoluidine, diglycidylmethoxyaniline, diglycidylphenylaniline, diglycidylethylaniline, diglycidyldimethylaniline, diglycidylamine. Examples thereof include glycidyl trifluoromethyl aniline. Examples of commercially available products include GAN and GOT (trade name, manufactured by Nippon Kayaku Co., Ltd.). These epoxy compounds have a very low viscosity and can be used as a reaction diluent as long as the heat resistance after curing is not impaired.

  Specific examples of the aminophenol type epoxy compound represented by the general formula (2) include p-aminophenol, m-aminophenol, o-aminocresol, trifluoromethylhydroxyaniline, hydroxyphenylaniline, methoxyhydroxyaniline, Examples thereof include triglycidylated butylhydroxyaniline. As commercial products, ELM120, ELM100 (above, trade name, manufactured by Sumitomo Chemical Co., Ltd.), “Araldite (registered trademark)” MY0500, “Araldite” MY0510 (above, trade name, manufactured by Vantico Co., Ltd.), “ jER (registered trademark) "630 (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.) and the like. These epoxy compounds have low viscosity, have a high density of epoxy groups in the compound, can increase the crosslinking density after curing, and are excellent in heat resistance after curing.

  Specific examples of the aromatic glycidylamine type epoxy compound represented by the general formula (3) include tetraglycidyldiaminodiphenyl ether, tetraglycidyltetramethyldiaminodiphenylether, tetraglycidyltetraethyldiaminodiphenylether, and tetraglycidylbis (aminophenoxyphenyl). Propane, tetraglycidylbis (aminophenoxyphenyl) sulfone, tetraglycidylbis (trifluoromethyl) diaminobiphenyl, tetraglycidylbenzidine, tetraglycidyltrizine, tetraglycidyldiaminodiphenylsulfone, tetraglycidyldiaminodiphenylmethane, α, α'-bis ( 4-aminophenyl) -1,4-diisopropylbenzene and epichlorohydrin 1: 4 addition reaction product Such as things. Commercially available products include ELM434 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), “Araldite (registered trademark)” MY720, “Araldite” MY721, “Araldite” MY722, “Araldite” MY9512, “Araldite” MY9612, “Araldite” MY9634, “Araldite” MY9663 (trade name, manufactured by Vantico), “jER (registered trademark)” 604 (produced by Japan Epoxy Resin), “Epiclon (registered trademark)” 430 (DIC) Etc.). These epoxy compounds have a slightly high viscosity, but have good storage stability, a large density of epoxy groups in the compound, a high crosslinking density after curing, and high heat resistance after curing. The toughness can be obtained with a good balance.

  Further, in order to further improve the curability, 6 such as hexaglycidyl bis (aminohydroxyphenyl) sulfone, hexaglycidyl bis (aminohydroxyphenyl) propane, hexaglycidyl bis (aminohydroxyphenyl) hexafluoropropane, etc. It may contain a functional epoxy compound.

  The underfill agent of the present invention contains 25 to 50% by weight of the epoxy compound represented by the general formula (1) in the total epoxy compound in order to achieve both low viscosity and heat resistance after curing at a higher level. It is preferable that the epoxy compound represented by the general formula (2) is contained in an amount of 20 to 40% by weight in all epoxy compounds. Furthermore, it is preferable to contain 20 to 40% by weight of the epoxy compound represented by the general formula (3) from the viewpoint of greatly improving heat resistance. It is preferable to contain all the epoxy compounds represented by (1) to (3) from the viewpoint of achieving both low viscosity and heat resistance after curing at a higher level.

  In addition to the epoxy compounds represented by these general formulas (1) to (3), other epoxy compounds can also be contained. Among such epoxy compounds, monofunctional epoxy compounds include 1,2-epoxypentane (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.), YED111N, YED122 (above, trade names, Japan Epoxy Resin Co., Ltd.). And Epolite M1230 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). As the bifunctional epoxy compound, EX-214L, EX-212L, EX-216L, EX-850L (above, trade name, manufactured by Nagase ChemteX Corporation), Epolite 40E, Epolite 100E, 200E, Epolite 400E, Epolite 200P, Epolite 400P, Epolite 3002, Epolite 80MF, Epolite 100MF, Epolite 4000, Epolite 70P, Epolite 1500NP, Epolite 1600 (above, product name, manufactured by Kyoeisha Chemical Co., Ltd.), Rica Resin DME-100 (trade name, Shin Nippon Rika ( YED216, YED216M (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), “jER (registered trademark)” 807, “jER” 828, “jER” 1002, “jER” 1750, “jER” 1007 YX-8100-BH30, E1256, E4250, E4275 (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.), “Epiclon (registered trademark)” EXA-9583, HP4032 (above, trade name, manufactured by DIC Corporation) NC3000, NC6000 (above, trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like. Examples of trifunctional epoxy compounds include “Denacol (registered trademark)” EX-321L (trade name, manufactured by Nagase ChemteX Corporation), VG3101 (trade name, manufactured by Mitsui Chemicals, Inc.), “Tepic (registered trademark)”. “S”, “Tepic” G, “Tepic” P (trade name, manufactured by Nissan Chemical Industries, Ltd.) and the like. Examples of tetrafunctional or higher functional epoxy compounds include PB3600, PB4700 (trade name, manufactured by Daicel Chemical Industries, Ltd.), Epototo (registered trademark) “YH-434L (above, trade name, manufactured by Toto Kasei Co., Ltd.), EPPN502H. (Trade name, manufactured by Nippon Kayaku Co., Ltd.), “Epiclon (registered trademark)” N695, HP7200 (above, product name, manufactured by DIC Corporation), “jER (registered trademark)” 1032 (above, product name, Japan Epoxy Resin Co., Ltd.), etc. Two or more of these epoxy compounds may be contained.

The epoxy compound (b) in the present invention has an SP value of 1.60 × 10 ^{4 to} 1.80 × 10 ⁴ (J / m ³ ) ^1/2 and an SP value of 2.00 × 10 ^4. It is necessary to contain at least one epoxy compound that is ˜2.60 × 10 ⁴ (J / m ³ ) ^1/2 . In the present invention, the toughness and heat resistance after curing can be improved by using (a) a polyethersulfone resin having a weight average molecular weight of 30,000 or more and the above epoxy resin.

  There are various methods for obtaining the SP value (solubility parameter value). In the present invention, the document “Polymer Engineering and Science (RF Fedors, Polymer. Eng., 14, (2) 147-154” is used. (1974) ”That is, in the structural formula of the compound to be obtained, the following formula is calculated from the evaporation energy and molar volume data of atoms and atomic groups.

In the above formula, Δe _i represents the evaporation energy at 25 ° C. belonging to the atom or group, Δv _i represents the molar volume at 25 ° C., and is a constant value given to i atoms and groups in the molecule. The values described in the above documents are used for Δe _i and Δv _i of typical atoms and groups.

As one method for improving toughness, it is known that the cured resin composition has a sea-island structure. An epoxy compound having an SP value of 2.00 × 10 ^{4 to} 2.60 × 10 ⁴ (J / m ³ ) ^1/2 is in phase with a polyethersulfone resin having a molecular weight of 30,000 or more as the component (a) in the present invention. The solubility is high, and it is easy to form a uniform phase between the epoxy compound and the polyethersulfone resin after curing. On the other hand, an epoxy compound having an SP value of 1.60 × 10 ^{4 to} 1.80 × 10 ⁴ (J / m ³ ) ^1/2 is a polyethersulfone having a molecular weight of 30,000 or more as the component (a) of the present invention. The compatibility with the resin is low, and the epoxy compound and the polyethersulfone resin tend to form a phase separation structure after curing. Therefore, a phase separation structure is easily formed between the polyethersulfone resin and the epoxy compound after curing, and the toughness after curing can be improved. Furthermore, an epoxy compound having the aforementioned SP value of 2.00 × 10 ^{4 to} 2.60 × 10 ⁴ (J / m ³ ) ^1/2 can improve heat resistance, and the aforementioned SP value is 1. The epoxy compound which is .60 × 10 ^{4 to} 1.80 × 10 ⁴ (J / m ³ ) ^1/2 can easily improve the low viscosity property. From the above, by containing one or more of these epoxy compounds, the toughness and heat resistance after curing can be improved, and low viscosity characteristics can be obtained more easily.

The SP value of ^{1.60 × 10 4 ~1.80 × 10 4} (J / m 3) epoxy compound is ^1/2, bifunctional aliphatic glycidyl ether epoxy resin is preferable, EX-212L ( SP value = 8.25 (cal / cm ³ ) ^1/2 = 1.69 × 10 ⁴ (J / m ³ )) ^1/2 ), EX-214L (SP value = 8.28 (cal / cm ³ )) ^1/2 = 1.69 × 10 ⁴ (J / m ³ ) ^1/2 ) , EX-850L (SP value = 8.42 (cal / cm ³ ) ^1/2 = 1.72 × 10 ⁴ (J / m ³ ) ^1/2 ) (above, trade name, manufactured by Nagase ChemteX Corp.), “Epicron (registered trademark)” 705 (SP value = 8.10 (cal / cm ³ ) ^1/2 = 1.66 × 10 ⁴ (J / m ³ ) ^1/2 ), “Epiclon” 707 (SP value = 7.98 ( cal / cm ³ ) ^1/2 = 1.63 × 10 ⁴ (J / m ³ ) ^1/2 ), “Epiclon” 720 (SP value = 8.45 (cal / cm ³ ) ^1/2 = 1.73 × 10 ⁴ (J / m ³ ) ^1/2 ), “Epiclon” 726 (SP value = 8.25 (cal / cm ³ ) ^1/2 = 1.69 × 10 ⁴ (J / m ³ ) ^1/2 ), EXA-4880 (SP value = 8.35 (cal / cm ³ ) ^1/2 = 1.71 × 10 ⁴ (J / m ³ ) ^1/2 ), EXA-4882 (SP value = 7.98 ( cal / cm ³ ) ^1/2 = 1.63 × 10 ⁴ (J / m ³ ) ^1/2 ) (trade name, manufactured by DIC Corporation), Epolite 40E (SP value = 8.33 (cal / ^{cm 3) 1/2 = 1.70 × 10} 4 (J / m 3) 1/2), Epolight 100E (SP value = 8.42 ( ^{al / cm 3) 1/2 = 1.72} × 10 4 (J / m 3) 1/2), Epolite 200E (SP value ^{= 8.50 (cal / cm 3)} 1/2 = 1.74 × 10 ⁴ (J / m ³ ) ^1/2 ), Epolite 400E (SP value = 8.58 (cal / cm ³ ) ^1/2 = 1.76 × 10 ⁴ (J / m ³ ) ^1/2 ), Epolite 70P (SP value = 8.13 (cal / cm ³ ) ^1/2 = 1.66 × 10 ⁴ (J / m ³ ) ^1/2 ), Epolite 200P (SP value = 8.10 (cal / cm ³ ) ^{1 / 2 = 1.66 × 10 4 (} J / m 3) 1/2), Epolite 400P (SP value ^{= 7.98 (cal / cm 3)} 1/2 = 1.63 × 10 4 (J / m 3 ) ^1/2), Epolight 1500NP (SP value ^{= 8.45 (cal / cm 3)} 1/2 = 1 ^{73 × 10 4 (J / m} 3) 1/2), Epolite 1600 (SP value ^{= 8.25 (cal / cm 3)} 1/2 = 1.69 × 10 4 (J / m 3) 1/2) (The above is a trade name, manufactured by Kyoeisha Chemical Co., Ltd.) , YED216 (SP value = 8.25 (cal / cm ³ ) ^1/2 = 1.69 × 10 ⁴ (J / m ³ ) ^1/2 ), YED216D (SP value = 8.25 (cal / cm ³ ) ^1/2 = 1.69 × 10 ⁴ (J / m ³ ) ^1/2 ), YED216M (SP value = 8.25 (cal / cm ³ ) ^{1 / 2} = 1.69 × 10 ⁴ (J / m ³ ) ^1/2 ) (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.) and the like. Two or more of these may be contained.

The epoxy compound having an SP value of 2.00 × 10 ^{4 to} 2.60 × 10 ⁴ (J / m ³ ) ^1/2 is preferably a bifunctional bisphenol type epoxy resin from the viewpoint of low viscosity. Also, from the viewpoint of heat resistance, phenol novolac type, cresol novolac type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin are preferable.

As the bifunctional bisphenol F type epoxy resin, “Epiclon (registered trademark)” 830 (SP value = 11.47 (cal / cm ³ ) ^1/2 = 2.35 × 10 ⁴ (J / m ³ ) ^{1 / 2} ) (above, trade name, manufactured by DIC Corporation), RE-303S (SP value = 11.47 (cal / cm ³ ) ^1/2 = 2.35 × 10 ⁴ (J / m ³ ) ^{1 / 2} ) (trade name, manufactured by Nippon Kayaku Co., Ltd.), “jER (registered trademark)” 806 (SP value = 11.50 (cal / cm ³ ) ^1/2 = 2.35 × 10 ⁴ (J / M ³ ) ^1/2 ), “jER” 807 (SP value = 11.50 (cal / cm ³ ) ^1/2 = 2.35 × 10 ⁴ (J / m ³ ) ^1/2 ) (above, product Name, manufactured by Japan Epoxy Resin Co., Ltd.), as bifunctional bisphenol A type epoxy resin, 84 0 (SP value = 12.31 (cal / cm ³ ) ^1/2 = 2.52 × 10 ⁴ (J / m ³ ) ^1/2 ), 850 (SP value = 12.31 (cal / cm ³ ) ^{1 / 2 = 2.52 × 10 4 (} J / m 3) 1/2), 860 (SP value ^{= 12.31 (cal / cm 3)} 1/2 = 2.52 × 10 4 (J / m 3) ^1/2 ) ((product name, manufactured by DIC Corporation)), RE-310S (SP value = 12.31 (cal / cm ³ ) ^1/2 = 2.52 × 10 ⁴ (J / m ³ ) ^1/2 ) (above, trade name, manufactured by Nippon Kayaku Co., Ltd.), “jER” 827 (SP value = 12.31 (cal / cm ³ ) ^1/2 = 2.52 × 10 ⁴ (J / m ^{3) 1/2), "jER"} 828 (SP value ^{= 12.31 (cal / cm 3)} 1/2 = 2.52 × 10 4 (J / m 3) 1/2) "JER" 834 (SP value ^{= 12.35 (cal / cm 3)} 1/2 = 2.53 × 10 4 (J / m 3) 1/2) ( trade names, manufactured by Japan Epoxy Resins Co., Ltd. ), As phenol novolac type epoxy resin, “Epiclon” N-540 (SP value = 12.66 (cal / cm ³ ) ^1/2 = 2.30 × 10 ⁴ (J / m ³ ) ^1/2 ), N-740, N-770 (both SP value = 11.30 (cal / cm ³ ) ^1/2 = 2.30 × 10 ⁴ (J / m ³ ) ^1/2 ), (above, trade name, DIC ), EPPN-201 (SP value = 11.26 (cal / cm ³ ) ^1/2 = 2.30 × 10 ⁴ (J / m ³ ) ^1/2 ) (above, product name, Nipponization (Manufactured by Yakuhin Co., Ltd.), "jER" 152, 154 (both SP values = 11.30 (ca ^{/ Cm 3) 1/2 = 2.30 ×} 10 4 (J / m 3) 1/2), as the cresol novolak type epoxy resin, "EPICLON" N-660, N-665 , N-670, N- 680, N-690 (both SP value = 10.28 (cal / cm ³ ) ^1/2 = 2.10 × 10 ⁴ (J / m ³ ) ^1/2 ) (above, trade name, DIC Corporation) Manufactured), EOCN-1020 (SP value = 10.40 (cal / cm ³ ) ^1/2 = 2.13 × 10 ⁴ (J / m ³ ) ^1/2 ), EOCN-102S (SP value = 10.44) (Cal / cm < ³ >) < ^1/2 > = 2.14 * 10 < ⁴ > (J / m < ³ >) < ^1/2 >), EOCN-103S (SP value = 10.48 (cal / cm < ³ >) < ^1/2 > = 2.14. × 10 ⁴ (J / m ³ ) ^1/2 ), EOCN-104S (SP value = 10. 52 (cal / cm ³ ) ^1/2 = 2.15 × 10 ⁴ (J / m ³ ) ^1/2 ) (above, trade name, manufactured by Nippon Kayaku Co., Ltd.), naphthalene type epoxy resin, “Epiclon” HP4700, EXA4710, HP4770 (all SP values = 1.09 (cal / cm ³ ) ^1/2 = 2.06 × 10 ⁴ (J / m ³ ) ^1/2 ), DIC Corporation), “jER” YX4000 (SP value = 9.89 (cal / cm ³ ) ^1/2 = 2.02 × 10 ⁴ (J / m ³ ) ^1/2 ) as a biphenyl type epoxy resin YL6121H (SP value = 11.44 (cal / cm ³ ) ^1/2 = 2.34 × 10 ⁴ (J / m ³ ) ^1/2 ) (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.) , NC3000, NC3000H (both SP ^{= 11.23 (cal / cm 3)} 1/2 = 2.30 × 10 4 (J / m 3) 1/2), manufactured (trade name, manufactured by Nippon Kayaku Co.) and the like. Two or more of these may be contained.

  Furthermore, in addition to the (b) epoxy compound, an oxetane compound can be contained. By containing the oxetane compound, the thermal stability is improved, so that the heat resistance after curing can be improved. Among such oxetane compounds, monofunctional oxetane compounds include etanacol (registered trademark) “EHO”, “etanacol” OXMA (above, trade name, manufactured by Ube Industries, Ltd.), OXT-101, OXT-211. , OXT-212, OXT-610 (above, trade name, manufactured by Toa Gosei Co., Ltd.), 3-ethyl-3- (cyclohexyloxy) methyloxetane, and bifunctional oxetane compounds include “Ethanacol” OXBP , "Ethanacol" OXTP, "Ethanacol" OXIPA (above, trade name, manufactured by Ube Industries, Ltd.), OXT-121, OXT-221 (above, trade name, manufactured by Toa Gosei Co., Ltd.), 3 or more oxetanyl Examples of the compound having a group include oxetaneated phenol resin, oxetanyl silicate, and phenol novolac type Kisetan compounds. May contain two or more kinds.

  The underfill agent of the present invention may contain 1% by weight or less of (c) a solvent for the purpose of adjusting the viscosity or improving the coating property. By setting the solvent content to 1% by weight or less, generation of voids due to solvent scattering during heat treatment can be suppressed, and storage stability can be improved without agglomerating the polyethersulfone resin particles. it can.

  Solvents include, for example, ketone solvents acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ether solvents 1,4-dioxane, tetrahydrofuran, diglyme, glycol ether solvents methyl cellosolve, ethyl cellosolve, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, aromatic hydrocarbon solvents benzene, xylene, toluene, other benzyl alcohol, propanol, N-methylpyrrolidone, γ-butyrolactone, ethyl acetate , N, N-dimethylformamide and the like. Two or more of these may be contained. In particular, it is preferable to use one having a boiling point under atmospheric pressure of 120 ° C. or lower because the solvent can be removed at a low temperature in a short time.

  The underfill agent of the present invention can contain (d) at least one inorganic fine particle selected from the group consisting of silica, titania, zirconia, silicon nitride, alumina, ceria, talc and calcium carbonate. By containing these inorganic fine particles, thermal conductivity can be imparted or the thermal linear expansion coefficient after curing can be reduced. In the case of imparting thermal conductivity, calcium carbonate, silica, alumina, titania, and silica-titania composite particles are preferable. Furthermore, in order to firmly bond the interface between the inorganic fine particles and the matrix resin, the surface of the inorganic fine particles is treated with various coupling agents such as silane, titanium and aluminum, fatty acids, phosphate esters, etc., or rosin treatment Those subjected to acidic treatment and basic treatment are also preferably used. A silane coupling agent is preferable in order to increase the affinity with the epoxy compound, and in particular, a silane coupling agent having an epoxy group is preferably used in terms of increasing toughness. Preferred examples of the silane coupling agent include γ-glycidoxytrimethoxysilane, γ-glycidoxytriethoxysilane, γ-glycidoxytripropoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-amino And propyltripropoxysilane. Two or more of these may be used.

  The content of the inorganic fine particles (d) is preferably 10 to 5000 parts by weight with respect to 100 parts by weight as a total of the polyethersulfone resin as the component (a) and the epoxy compound as the component (b). When the content of the inorganic fine particles is 10 parts by weight or more, the thermal conductivity can be improved or the thermal linear expansion coefficient can be further reduced. By setting the content to 5000 parts by weight or less, the viscosity of the underfill agent is increased. Can be prevented. More preferably, it is 20 parts by weight or more and 500 parts by weight or less.

  The average particle size of the inorganic fine particles is preferably 5 nm to 30 μm, more preferably 5 nm to 10 μm. Here, the average particle diameter in the present invention is obtained by using a transmission electron microscope (H-7100FA type, manufactured by Hitachi, Ltd.) as a cross section of a coating film having a thickness of 20 μm prepared using an ultrathin section method. Observation is performed at an observation magnification of 200000 times under the condition of an acceleration voltage of 100 kV, and the particle diameter of each individual particle is measured from the obtained image, and the number average value thereof is obtained. The number of particles used for measurement is several hundred to several thousand. When the average particle size is 5 nm or more, it is possible to obtain an appropriate viscosity and at the same time obtain stable particle dispersibility. By setting the average particle size to 30 μm or less, the low viscosity property is improved and the sedimentation of inorganic fine particles is prevented. Can do.

  The underfill agent of the present invention can contain (e) at least one organic fine particle selected from the group consisting of polyimide, polyamide, polyamideimide, polystyrene, polyacrylonitrile, polyphenylene ether, polyester and polycarbonate. By containing these organic fine particles, heat resistance and low hygroscopicity can be imparted.

  The content of these (e) organic fine particles is preferably 5 to 5000 parts by weight with respect to 100 parts by weight as a total of the polyethersulfone resin as the component (a) and the epoxy compound as the component (b). When the content of the organic fine particles is 5 parts by weight or more, heat resistance and low hygroscopicity can be easily imparted, and when the content is 5000 parts by weight or less, an increase in the viscosity of the resin composition can be prevented. .

  The average particle size of the organic fine particles is preferably 5 nm to 10 μm, more preferably 5 nm to 5 μm. The method for measuring the average particle size of the organic fine particles is the same as the method for measuring the average particle size of the inorganic fine particles.

  In addition, phenoxy resin, polyurethane, polypropylene, acrylonitrile-butadiene copolymer (NBR), styrene-butadiene copolymer, (SBR), acrylonitrile-butadiene-methacrylic acid copolymer, acrylonitrile-butadiene-acrylic acid copolymer, etc. It may contain.

  The underfill agent of the present invention can further contain a curing agent and a curing accelerator. Here, the curing agent refers to an agent that has an effect of curing alone, and the curing accelerator refers to an agent that has an effect of promoting the reaction when used together with the curing agent. Curing agents or curing accelerators that can be used in the underfill agent of the present invention include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, acid anhydrides, phenol resins, dicyandiamide and derivatives thereof, and imidazoles and derivatives thereof. Condensates of amine derivatives and formaldehyde (urea formaldehyde, melamine formaldehyde), tertiary amine compounds, organometallic complexes, polythiols, onium salts and the like. Two or more of these may be contained.

  Specifically, examples of the aliphatic polyamine include diethyltriamine, triethylenetetramine, and xylenediamine. Examples of the alicyclic polyamine include isophoronediamine, 1,3-bisaminomethylcyclohexane, and norbornenediamine. Phenoxy diamines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and bisaminophenoxybenzene. Acid anhydrides include succinic anhydride, itaconic anhydride, phthalic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, methylhexahydrophthalic anhydride , Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, “ADEKA HARDNER (registered trademark)” EH-3326, “ADEKA HARDNER” EH-703, “ADEKA HARDNER” EH-705A (above, trade name, Asahi Denka Kogyo Co., Ltd.), "Epiclon" B-570, "Epicron" B-650 (above, trade name, manufactured by Dainippon Ink and Chemicals), "Licacid (registered trademark)" MH-700 (Product) Name, manufactured by Shin Nippon Rika Co., Ltd.). Examples of the phenol resin include various phenol novolac resins, cresol novolac resins, MEH-7500, MEH-7800, MEH-7851, MEH-8000H (above, trade names, manufactured by Meiwa Kasei Co., Ltd.) and the like. As dicyandiamide and derivatives thereof, DICY7, DICY15, DICY50 (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.), “Amure (registered trademark)” AH-154, “Amure” AH-162 (above, trade name, Ajinomoto Fine Techno Co., Ltd.). Examples of imidazoles and derivatives thereof include imidazole, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxy. Imidazole, imidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, IS-1000, IS-1000D, IM-1000, SP-1000, IA-100A, IA-100P, IA-100F ( Less than , Trade name, manufactured by Nikko Materials Co., Ltd.), and the like imidazole silane, such as. Examples of the condensate of amine derivative and formaldehyde (urea formaldehyde, melamine formaldehyde) include 4-chloro-phenyl-N, N-dimethylurea and 3,4-dichlorophenyl-N, N-dimethylurea (DCMU). Tertiary amine compounds include 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU), 1,5-diazabicyclo (4,3,0) -nonene-5 (DBN) and salts thereof. Specifically, U-CATSA1 (DBU-phenol salt), U-CAT SA102 (DBU-octylate), U-CATSA603 (DBU-formate), U-CAT SA810 (DBU-orthophthalate) ), U-CATSA841 (DBU-phenol novolac resin salt), U-CAT SA881 (DBN-phenol novolac resin salt) (above, trade name, manufactured by San Apro Co., Ltd.) and the like. Examples of organometallic complexes include triphenylphosphine and triphenylphosphonium triphenylborate, and examples of polythiols include aliphatic polythioethers, aliphatic polythioesters, and aromatic ring-containing polythioethers. Examples of onium salts include onium salts such as sulfonium and iodonium, and onium salt-type diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, Syracure UVI-6992, Syracure UVI-6974 (above, trade names, Dow Chemical Japan Co., Ltd.), Adekaoptomer SP150, Adekaoptomer SP170 (above, trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), Sun-Aid SI-60L, SI-80L, SI-100L, SI-150L (The above is a trade name, manufactured by Sanshin Chemical Industry Co., Ltd.).

  In addition, as an example of a latent curing agent that can be stored for a long time in a state mixed with an epoxy compound and initiates a curing reaction when stimulated by heat, light, pressure, moisture, etc., a thermosetting latent curing agent, Examples include a microcapsule type latent curing agent and an amine adduct type latent curing agent. Specific examples of the heat curable latent curing agent include dicyandiamide and 3,4-dichlorophenyl-N, N-dimethylurea (DCMU). The microcapsule-type latent curing agent is a curing agent having a core (core material) / shell (capsule film) structure. Examples of the core include various imidazole compounds and triphenylphosphine, and examples of the shell include organic polymers and inorganic compounds. Specific examples include “Novacure (registered trademark)” HX-3941HP, “Novacure” HXA3922HP, “Novacure” HXA3932HP, “Novacure” HXA3042HP (trade name, manufactured by Asahi Kasei Chemicals Corporation).

  The amine adduct type latent curing agent is a pulverized product obtained by reacting an imidazole compound, a tertiary amino group-containing compound or a hydrazide compound with an epoxy compound or an isocyanate compound to obtain a high molecular weight, and has a solubility at room temperature. Is low and shows potential. Specifically, “Amicure” PN-23, “Amicure” PN-40, “Amicure” MY-24, “Amicure” MY-H (trade name, manufactured by Ajinomoto Fine Techno Co., Ltd.), “Fujicure ( Registered trademark) "FXR-1030 (trade name, manufactured by Fuji Kasei Co., Ltd.)", "Amicure" VDH, "Amicure" UDH (trade name, manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like.

  In the present invention, an aromatic polyamine and a microcapsule-type latent curing agent are preferable from the viewpoint of good curability to an underfill agent, and an aromatic polyamine is more preferable from the viewpoint of good storage stability and dispersibility. preferable. Examples of such aromatic polyamines include metaphenylenediamine, paraphenylenediamine, 2,4-toluenediamine, 2,5-toluenediamine, dimethyltoluenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, 4 , 4′-diamino-3,3′-dimethyl-diphenylmethane, 3,3′-diamino-4,4′-dimethyl-diphenylmethane, 4,4′-diamino-3,3′-dichloro-diphenylmethane, 3,3 '-Diamino-4,4'-dichloro-diphenylmethane, 4,4'-diamino-3,3', 5,5'-tetramethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane 4,4′-diamino-3,3 ′, 5,5′-tetraethyl-diphenylmethane, 3, '-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, bis (p- (m-aminophenoxy) phenyl) sulfone, bis (p -(P-aminophenoxy) phenyl) sulfone, 3,3'-bis (p-aminophenoxy) biphenyl, 2,2'-bis (p-aminophenoxy) phenyl) -1,1,1,3,3 3-hexafluoropropane, 4,4′-bis (m-aminophenoxy) biphenyl, m-bis (p-aminophenoxy) benzene, p-bis (p-aminophenoxy) benzene, m-bis (m-aminophenoxy) ) Benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, p-bis (p-amino) Phenoxy) diphenyl ether, p- bis (m-aminophenoxy) diphenyl ether, bis (p-(p-aminophenoxy) phenoxy) benzene, and the like. Of these, aromatic sulfone diamines are preferably used because they have a high melting point and good storage stability. Examples of the aromatic sulfone-based diamine include 3,3′-diaminodiphenyl sulfone and 4,4′-diaminodiphenyl sulfone, and examples of commercially available products include Seika Cure S (trade name, manufactured by Seika Co., Ltd.).

  The phenoxy-based diamine has an ether bond, can prevent a decrease in Tg due to the influence of humidity, and can improve the moisture resistance after curing. Furthermore, the phenoxy-type diamine represented by the following general formula (7) has an effect of greatly reducing the viscosity of the underfill agent at room temperature and high temperature.

In the general formula (7), a represents an integer of 2 to 4. R ^{26 to} R ²⁹ represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, a fluoroalkyl group, or an aryl group, and may be the same or different. The alkyl group may be linear or cyclic.

The phenoxy-based diamine represented by the general formula (7) has an SP value of SP value of 1.60 × 10 ^{4 to} 1.80 × 10 ⁴ (J / m ³ ) ^1/2 , in particular. Is preferably used in combination with an epoxy compound having a ratio of 2.00 × 10 ^{4 to} 2.60 × 10 ⁴ (J / m ³ ) ^1/2 and the toughness after curing can be improved. Examples of the phenoxy diamine represented by the general formula (7) include m-bis (p-aminophenoxy) benzene, p-bis (p-aminophenoxy) benzene, m-bis (m-aminophenoxy) benzene, 3 , 3′-bis (3 ″ -aminophenoxy) diphenyl ether, 4,4′-bis (3 ″ -aminophenoxy) diphenyl ether, bis (p- (p-aminophenoxy) phenoxy) benzene, bis (m- (m- Aminophenoxy) phenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene and the like, and commercially available products such as APB, APB-N, APB-NP, APB-5 (and above, trade names) , Manufactured by Mitsui Chemicals, Inc.), TPE-R, TPE-Q (above, trade name, manufactured by Wakayama Seika Kogyo Co., Ltd.), 4-APB, 3, 4'- APE, 3-APB, AHPB (or more, trade name, manufactured by Nippon Junryo Pharmaceutical Co., Ltd.), and the like.

  In addition, as a curing accelerator preferably used in the present invention, 3-phenyl-N, N-dimethyl, which is a thermosetting latent curing agent, can be mixed with a polyethersulfone resin and an epoxy compound in an incompatible state at room temperature. Examples include urea, 4-chlorophenyl-N, N-dimethylurea, 3,4-dichlorophenyl-N, N-dimethylurea, and 3-chloro-4-methylphenyl-N, N-dimethylurea.

  In the underfill agent of the present invention, the content of the curing agent is preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the total amount of the polyethersulfone resin as the component (a) and the epoxy compound (b). By setting the content of the curing agent to 0.1 parts by weight or more, the epoxy compound is effectively cured, and by setting the content to 60 parts by weight or less, it is possible to prevent the viscosity of the cured product from being increased.

  The shape of the curing agent is not particularly limited even if it is liquid or solid, but in the case of a solid, a powder is preferable from the viewpoint of dispersibility and solubility. Moreover, when using a microcapsule type | mold latent hardener, 5 nm-10 micrometers are preferable, and, as for the average particle diameter of a hardener, More preferably, they are 5 nm-5 micrometers. The measurement of the average particle diameter is the same as the method for measuring the average particle diameter of the inorganic fine particles.

  The thermosetting resin composition of the present invention may further contain a thermal crosslinking agent. Examples of the thermal crosslinking agent include a compound having an ethynyl group, a vinyl group, a methylol group, a methoxymethylol group, or a benzoxazine compound. Furthermore, you may contain the compound which has the hardening function of a thermal crosslinking group and an epoxy compound like maleic anhydride, an ethynyl phthalic anhydride, an ethynyl aniline, a vinyl aniline.

  In addition, the underfill agent of the present invention contains nonionic, cationic, anionic surfactants, wetting agents such as polyvalent carboxylic acids, amphoteric substances, resins having highly sterically hindered substituents, and the like. May be. Moreover, you may contain a stabilizer, a dispersing agent, an anti-settling agent, a plasticizer, antioxidant, etc. as needed.

In general, when used as an underfill agent, the gap between the semiconductor element and the substrate is within a temperature range of 70 to 120 ° C., which is the substrate temperature, and the minimum value of the viscosity is 1.0 × 10 ² Pa · s or less. Can be quickly filled. For this reason, the underfill agent of the present invention has a minimum viscosity η ^* of 1.0 × 10 ² Pa · in a viscoelasticity-temperature curve obtained by dynamic viscoelasticity measurement (temperature increase rate 2 ° C./min). It is preferable that the temperature which is below s and shows the minimum value of a viscosity is 70-120 degreeC. More preferably, it is 1.0 × 10 Pa · s or less.

The viscosity of the underfill agent is determined by dynamic viscoelasticity measurement using a parallel disk type measurement system. In the case of the parallel disk type, a sample is filled between both disks, and one disk is vibrated at a constant frequency, and the rigidity, viscosity, and tan δ are obtained from the torque and phase difference generated in the other disk. The viscosity here indicates a complex viscosity obtained by measurement, and its unit is Pa · s. In the present invention, the measurement is performed under conditions of an amplitude of 0.5 deg, an angular frequency of 3 s ⁻¹ , a frequency of 0.5 Hz, a measurement temperature of 25 ° C. to 170 ° C., a temperature increase rate of 2 ° C./min, and an N ₂ gas stream.

In order to obtain an underfill agent having such viscosity characteristics, the content of the polyether resin as the component (a) is preferably 40% by weight or less, more preferably 30% by weight or less, and 20% by weight or less. Is more preferable. Moreover, as a reaction diluent, it is preferable to use the epoxy compound which has low viscosity, for example, the epoxy compound represented by the said General formula (1). The epoxy compound having low viscosity preferably has a viscosity of less than 200 mPa · s at 25 ° C. and 1.013 × 10 ⁵ N / m ² . Specific examples of the epoxy compound having a viscosity of less than 200 mPa · s at 25 ° C. and 1.013 × 10 ⁵ N / m ² include YED216M, YED216D, YED111N, and YED122N (trade names, manufactured by Japan Epoxy Resins Co., Ltd.). Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (above, trade name, manufactured by Kyoeisha Chemical Co., Ltd.), EX-214L , EX-212L, EX-216L, EX-850L (above, trade name, manufactured by Nagase ChemteX Corporation), “Epicron (registered trademark)” EXA-4880, “Epicron” 520, “Epicron” 70 , "EPICLON" 705, "EPICLON" 725, "EPICLON" 727, (trade names, DIC (Ltd.)) or, the epoxy compounds represented by the general formula (1). Of these, GAN and GOT (trade names, manufactured by Nippon Kayaku Co., Ltd.) are specifically preferable. The viscosity can also be lowered by containing a monovalent oxetane compound such as hydroxymethyl oxetane, ethyl oxetane methanol, or methyl oxetane methanol.

  Other methods for adjusting the viscosity of the underfill agent to the above range include a method using a phenoxy-based diamine represented by the general formula (7) as a curing agent, and greatly reducing the viscosity from room temperature to high temperature. it can.

  In order to set the reaction start temperature of the underfill agent to around 70 ° C., amines such as aliphatic polyamines and secondary amines, and imidazoles are preferably used as the curing agent. Moreover, in order to make reaction start temperature 70-120 degreeC vicinity, a secondary amine, tertiary amine, an aromatic amine, and a microcapsule type | mold latent hardening | curing agent are used suitably. Furthermore, when it is desired to initiate the curing reaction at a temperature exceeding 120 ° C., DCMU, DCMU type latent curing agent, DICY (dicyandiamide), DICY type latent curing agent, and the like are preferably used. Moreover, you may adjust a cure rate by containing 2 or more types of hardening | curing agents, or combining with a hardening accelerator.

  The underfill agent of the present invention preferably has a glass transition temperature after curing of 100 ° C. or higher, more preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and 200 ° C. or higher, as an indicator of heat resistance after curing. Is more preferable. Such a glass transition temperature is caused by (a) a high glass transition temperature of a polyethersulfone resin having a weight average molecular weight of 30,000 or more and a glass transition temperature of an epoxy compound.

The fracture toughness value K1c after curing of the underfill agent of the present invention is preferably 1.5 MPa · m ^1/2 or more, more preferably 2.0 MPa · m ^1/2 or more. If the fracture toughness value K1c is 1.5 MPa · m ^1/2 or more, the connection reliability and thermal shock resistance between the semiconductor element and the substrate after curing of the underfill agent of the present invention can be improved.

The method for measuring and calculating the fracture toughness value is defined by ASTM D5045-93 [Plane strain fracture toughness and strain energy release rate of plastic material] (= ISO13586). In the present invention, a preliminary crack is put in a test piece having a thickness of 6 mm, a width of 12 mm, and a length of 52.8 mm, and a test temperature of 23 ° C. and a crosshead speed of 10 mm / The three-point bending test is performed at an edge span interval of 48 mm, and the fracture toughness value K1c is obtained from the maximum fracture load. The equation for obtaining the value of K1c is represented by the following equation, and the unit is MPa · m ^1/2 .
_{K1c = P max Sf (a /} W) / BW 3/2
Where P _max is the maximum breaking load [kN], S is the span distance (distance between the jig rollers) [cm], a is the crack length [cm], W is the specimen width [cm], and B is the specimen. The thickness is [cm]. Further, f (a / W) is set to a / W = X and S / W = 4.0, and f (X) is obtained by the following equation.

  In order to obtain an underfill agent having such a fracture toughness value, for example, the weight average molecular weight of the polyethersulfone resin as the component (a) is preferably 30,000 or more. More preferably, it is 50,000 or more. Furthermore, a glycidylamine type epoxy compound, particularly an aromatic glycidylamine type epoxy compound is preferred in order to increase the glass transition temperature and achieve both heat resistance and toughness at a higher level. Examples of such aromatic glycidylamine type epoxy compounds include compounds represented by the following general formula (2) or (3). Specific examples include “jER” 604, “jER” 630 (above, trade name, manufactured by Japan Epoxy Resins Co., Ltd.) and the like. In addition, the fracture toughness value can be increased by containing an epoxy compound having a bisphenol structure, a glycidyl ether type epoxy compound of phenols such as phenol novolak and cresol novolak, and a naphthalene-containing type epoxy compound. In particular, a bisphenol skeleton is preferable because it provides toughness. Specific examples of the bisphenol type epoxy compound include “jER” 807, “jER” 828 (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.), Epolite 3002 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and the like. It is done.

Moreover, in order to achieve both toughness and low viscosity characteristics at a higher level, the epoxy compound of component (b) has an SP value of 1.60 × 10 ^{4 to} 1.80 × 10 ⁴ (J / m ³ ). Each containing one or more epoxy compounds having an SP value of ^1/2 and an epoxy compound having an SP value of 2.00 × 10 ^{4 to} 2.60 × 10 ⁴ (J / m ³ ) ^1/2 , It is preferable to contain a phenoxy diamine represented by the general formula (7).

  The underfill agent of the present invention can be obtained, for example, by mixing the polyethersulfone resin as the component (a) and the epoxy compound as the component (b) and dispersing them in an incompatible state. The dispersion method is not particularly limited, and examples thereof include ultrasonic dispersion, ultrasonic dispersion, ball mill, roll mill, kneader, clear mix, homogenizer, and media disperser. (A) It is preferable to perform stirring of a component at 40 degrees C or less, and 25 degrees C or less is more preferable.

  (B) There are two types of epoxy compounds, liquid and solid. In the case of a solid epoxy compound, it may be dissolved in advance in a liquid epoxy compound. In this case, it is preferable to heat-dissolve in a temperature range from room temperature to 150 ° C, preferably from 30 ° C to 100 ° C.

  In the case of containing an epoxy component other than (b), organic / inorganic fine particles, a curing agent, a curing accelerator and the like, after mixing the polyethersulfone resin of the component (a) and the epoxy compound of the component (b) These are preferably added and mixed.

  The addition method of the curing agent and the curing accelerator is not particularly limited, but the curing agent and the curing accelerator having high reactivity may be dispersed and dissolved in the resin composition at room temperature, or the curing agent and curing acceleration having low reactivity. The agent may be heat-dissolved in the resin composition. In the case of heat melting, stirring is preferably performed in a temperature range of 30 ° C. to 180 ° C. for 0.5 hour to 8 hours, and more preferably in a range of 50 ° C. to 80 ° C. for 1 hour to 2 hours.

  The order of addition of the curing agent and the curing accelerator is not particularly limited, but the curing agent and the curing accelerator having high reactivity are preferably added last in consideration of storage stability. On the other hand, a curing agent and a curing accelerator having low reactivity may be added to an epoxy compound in advance and dissolved.

  When inorganic fine particles or organic fine particles are contained, the dispersion method is not particularly limited, but it is particularly preferable to use a ball mill or a homogenizer from the viewpoint of dispersibility.

  In order to improve the dispersibility of the inorganic fine particles, for example, a dispersant, a surfactant, or a solvent may be added. Examples of the dispersant include a dispersant having an acid group such as phosphoric acid, carboxylic acid, fatty acid, and esters thereof. In particular, a phosphoric acid compound is preferably used because it reacts with the hydroxyl groups on the surface of the inorganic fine particles to cover the particle surface.

  The underfill agent of the present invention is suitably used as an adhesive (underfill agent) for joining a semiconductor element and a substrate. In addition, the film obtained by curing the underfill agent of the present invention includes a protective film for semiconductor elements, an interlayer insulating film for multilayer wiring for high-density mounting, an interlayer insulating film for build-up printed wiring boards, and a circuit board. It can also be used for applications such as a wiring protective insulating film.

  The underfill agent filling method of the present invention is generally a method of dropping the underfill agent into the gap between the semiconductor element and the substrate, and other methods such as applying by a dispenser method or a printing method. The filling rate of the underfill agent after coating is preferably 0.5 cm / min or more, more preferably 1.0 cm / min or more.

  In the underfill agent of the present invention, the polyethersulfone resin is dissolved in the epoxy compound by heat treatment, and then the curing reaction is started. The dissolution condition of the underfill agent of the present invention is preferably 1 minute to 3 hours in a temperature range of 50 ° C to 250 ° C. If it is below 50 ° C., it may be difficult to dissolve. Considering the curing reactivity of the epoxy compound, it is more preferable to dissolve the epoxy compound in a temperature range of 50 ° C to 160 ° C. Moreover, the temperature at the time of preserving the underfill agent of this invention has the preferable range of -10-25 degreeC, More preferably, it is 9 degrees C or less, More preferably, it is 5 degrees C or less.

  Even when the polyethersulfone resin is dissolved in an epoxy compound and then applied, the underfill agent of the present invention is applied to a substrate in which a solution in which the polyethersulfone resin is in the form of particles and dispersed in the epoxy compound is set to a preset temperature. It can be applied and then dissolved. Since the curing reaction starts gradually after being dissolved once, it is preferably applied for 0.1 seconds to 30 minutes after dissolution.

  The underfill agent of the present invention is filled in the gap between the semiconductor element and the substrate and cured. The underfill agent is usually cured at a temperature of room temperature to 250 ° C for 0.5 minutes to 10 hours, but it is cured at a low temperature to prevent damage to other electronic components and shorten line tact. And shorter time are desirable. The curing condition of the underfill agent of the present invention is preferably 30 minutes to 5 hours in a temperature range of 160 ° C to 250 ° C. Other curing conditions include a method of curing at a low temperature from 50 to 160 ° C. to a medium temperature for 1 to 100 hours and a method of curing at a high temperature of 250 to 300 ° C. for 1 second to 3 hours. It may be performed at a low temperature to a medium temperature of ˜160 ° C. for 1 minute to 1 hour.

  In the semiconductor device using the underfill agent of the present invention, the underfill agent is located between the semiconductor element and the substrate. As a preferable manufacturing example of a semiconductor device, a substrate element having bumps is bonded to a wiring substrate surface, and an underfill agent is filled in a gap between the semiconductor element and the substrate at the same time as bonding or after bonding, and is thermally cured to form a semiconductor. There is a method of obtaining a semiconductor device in which an element and a substrate are fixed. In addition, as an example of manufacturing to replenish the underfill agent first, the underfill agent is first applied to the surface of the wiring board by a dispenser method or a printing method, and then a semiconductor element having bumps is joined to the substrate, simultaneously with the joining, Alternatively, there is a method of obtaining a semiconductor device in which a semiconductor element and a substrate are fixed by thermally curing an underfill agent after bonding.

  Hereinafter, the present invention will be described with reference to examples and techniques, but the present invention is not limited to these examples. In addition, the measurement and evaluation in an Example were performed with the following method.

(1) Measurement of molecular weight of polyethersulfone resin NMP (LiCl (0.05 mol / L)) / H was measured by a system controller Waters 2690 (manufactured by Waters Co., Ltd.) by gel permeation chromatography (GPC) method. ₃ The molecular weight of the polyethersulfone resin was measured using a developing solvent of PO ₄ (0.05 mol / L) = 10/1 under the conditions of 0.4 mL / min, and the weight average molecular weight ( Mw) was calculated.

(2) Measurement of glass transition temperature A solution was prepared by adding NMP to the underfill agent to a solid content concentration of 70% by weight, and then applied by spin coating, and then a hot plate at 120 ° C. (Dainippon Screen Manufacturing Co., Ltd.) The prebaked film having a thickness of 10 μm ± 1 μm was prepared by baking with SKW-636 (manufactured by Co., Ltd.) for 3 minutes. This film was put into an inert oven (INH-21CD manufactured by Koyo Thermo System Co., Ltd.), raised to a curing temperature of 170 ° C. over 80 minutes, and heat-treated at 170 ° C. for 120 minutes. Thereafter, the oven was gradually cooled to 50 ° C. or lower to obtain a cured film. Next, the cured film on the obtained silicon wafer was immersed in 47 wt% hydrofluoric acid for 7 minutes at room temperature, then washed with tap water, and carefully peeled from the silicon wafer so as not to be broken.

  10 mg of the cured film obtained by the above method was put in an aluminum cell and sealed to obtain a measurement sample. Using a differential scanning calorimeter DSC-50 (manufactured by Shimadzu Corporation), the temperature was raised to 300 ° C. at a temperature rising rate of 5 ° C./min under the condition of a nitrogen flow rate of 20 ml / min. The measurement was again performed in the temperature range of 30 ° C. to 300 ° C. at a temperature rising rate of 20 ° C./min. The temperature at the minimum point of dDSC / dt was taken as the glass transition temperature.

(3) Measurement of terminal hydroxyl group content JEOL EX-270 type (270 MHz) was used as the measuring instrument by the nuclear magnetic resonance spectrum ( ¹ H-NMR) measurement method. CDCl ₃ and DMSO were used as measurement solvents, and heavy water (D ₂ O) was used as required. When CDCl ₃ was used, the chemical shift σ7.26 PPM was used as a reference, and when DMSO was used, the chemical shift σ2.5 PPM was used as a reference. About 2 drops of the sample was put into the sample tube, the measurement solvent was added so that the height was about 4 cm from the bottom of the sample tube, and heavy water was shaken up and down as necessary to prepare a measurement sample. The terminal hydroxyl group content (mol%) was determined from the integrated intensity ratio of the hydrogen atom of the aromatic ring derived from the polymer unit whose chemical shift is shifted to σ7.50 to σ6.50PPM and the detected peak of the terminal phenolic hydroxyl group.

(4) Viscosity characteristics measurement An underfill agent was filled between two parallel circular plates so that the distance between two disc-shaped aluminum disposable parallel plates with a diameter of 25 mm was 0.5 mm, and then the AR-G2 rheometer. A viscoelasticity-temperature curve at 25 to 170 ° C. was measured under the conditions of a temperature increase rate of 2 ° C./min and an angular frequency of 3 s ⁻¹ (frequency is 0.5 Hz) (manufactured by TA Instruments). .

(5) Evaluation of solubility The underfill agent was put into a glass screw tube, and each sample was allowed to stand at 23 ° C. for 6 hours and then observed with the naked eye to evaluate the solubility of the underfill agent. Incompatible with the whole, in which the polymer is evenly dispersed, incompatible, and in some places the polymer is slightly non-uniformly dissolved and partially agglomerated, partially compatible, overall uniform The solution in which the polymer was dissolved was defined as dissolution.

(6) Measurement of storage stability An underfill agent was put into a glass screw tube, each sample was measured for viscosity η ₀ at 23 ° C. and allowed to stand for 2 weeks, and then again at room temperature using the method (3) above. Viscosity η ₁ was measured and the thickening rate (%) was calculated according to the following formula. The case where the viscosity did not change was rated as ◯, and the case where the viscosity was increased by 30% or more was rated as x.
Thickening rate (%) = [(η ₁ −η ₀ ) / (η ₀ )] × 100.

(7) Measurement of curing start temperature 10 mg of the cured film obtained by the method described in (2) above was placed in an aluminum cell and sealed to obtain a measurement sample. Using a differential scanning calorimeter DSC-50 (manufactured by Shimadzu Corporation), the calorific value is measured at a temperature rising rate of 5 ° C./min and a temperature range of 20 ° C. to 300 ° C. under a nitrogen flow rate of 20 ml / min. It was. The curing start temperature was determined as follows using the obtained chart. For example, FIG. 1 is a DSC curve of the underfill agent G-1 of Example 7. In FIG. 1, the DSC curve 1 has a straight line portion L ₁ recognized in a temperature range of 25 to 140 ° C. and a straight line portion L ₂ recognized until reaching the peak P after rising. A straight line 2 is the extension line of L _1, and the intersection 4 of the straight line 3 which is extended line of L ₂ and a curing initiation temperature of the underfill agent G-1.

(8) Measurement of fracture toughness value Fracture toughness value K1c was measured according to ASTM D5045. That is, the underfill agent was poured into a mold made of “Teflon (registered trademark)”, put into an inert oven (INH-21CD manufactured by Koyo Thermo System Co., Ltd.), and raised to a curing temperature of 170 ° C. over 80 minutes. Heat treatment was performed at 170 ° C. for 120 minutes. Then, it annealed until the inside of oven became 50 degrees C or less, and obtained hardened | cured material. The obtained cured product was cut out with an autocutter to obtain a sample piece having a thickness of 6 mm, a width of 12 mm, and a length of 52.8 mm, and further a preliminary crack was put therein, using a Tensilon universal testing machine (manufactured by A & D Corporation). A three-point bending test was performed under the conditions of a temperature of 23 ° C., a crosshead speed of 10 mm / min, and an edge span interval of 48 mm, and the fracture toughness value K1c (MPa · m ^1/2 ) was determined from the measured maximum fracture load. . The equation for obtaining the value of K1c is represented by the following equation.
_{K1c = P max Sf (a /} W) / BW 3/2
Where P _max is the maximum breaking load [kN], S is the span distance (distance between the jig rollers) [cm], a is the crack length [cm], W = test specimen width [cm], B = test specimen The thickness is [cm]. Further, f (a / W) is set to a / W = X and S / W = 4.0, and f (X) is obtained by the following equation.

(9) Evaluation of voids An underfill agent was filled in a gap between a polyimide substrate on which a copper circuit was formed and a semiconductor element mounted on the substrate, and then cured by heating at 170 ° C. for 1 hour. The presence or absence of voids having a diameter of 3 μm or more was examined using a semiconductor inspection apparatus C-SAM (manufactured by SONIX). The measurement range was 3 mm × 3 mm.

(10) Measurement of average thermal linear expansion coefficient The cured film obtained by the method described in (2) above was cut into 3 mm × 17 mm, and a thermomechanical analyzer SS-6100 (manufactured by Seiko Instruments Inc.) was used. The elongation of the cured film was measured under the following conditions: tensile mode, temperature range 25-170 ° C., temperature rising rate 5 ° C./min, initial load 0.5 g, and chuck interval 15 mm. From the obtained measurement results, the average coefficient of thermal expansion at T _{1 to} T ₂ ° C. was calculated using the following formula. Here, LT ₁ is the sample length at T ₁ ° C, and LT ₂ is the sample length at T ₂ ° C.
Average coefficient of thermal linear expansion = (1 / LT ₁ ) [(LT ₂ −LT ₁ ) / (T ₂ −T ₁ )].

(11) Calculation of SP value The SP value is determined by the method described in the document "Polymer Engineering and Science (RF Fedors, Polymer. Eng., 14, (2) 147-154 (1974)". That is, in the structural formula of the desired compound, the following formula was calculated from the evaporation energy and molar volume data of atoms and atomic groups.

However, .DELTA.e _i is evaporation energy at 25 ° C. attributable to atoms or groups, the Delta] v _i indicate the molar volume at 25 ° C.. The values described in the above literature were used for Δe _i and Δv _i of typical atoms and groups.

Synthesis Example 1: Synthesis of polyethersulfone resin A (direct polymerization method)
25.02 g of 4,4′-dihydroxydiphenylsulfone (0.1 mol, manufactured by Wako Pure Chemical Industries, Ltd.) in a 500 mL three-necked flask equipped with a nitrogen introducing tube, a stirring rod, and a thermometer under a dry nitrogen stream 4,4'-dichlorodiphenylsulfone 28.72 g (0.1 mol, manufactured by Wako Pure Chemical Industries, Ltd.) and anhydrous potassium carbonate 27.6 g (0.2 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) Was dissolved in 440 g of NMP (Mitsubishi Chemical Corporation) and 49 g of toluene (Tokyo Chemical Industry Co., Ltd.), and the temperature of the solution was reacted at 150 ° C. for 6 hours. Thereafter, cooling was performed, and when the temperature of the solution decreased to room temperature, the solution was poured into 3 L of methanol to obtain a white polymer solid. The polymer solid was collected by filtration, further washed with methanol twice, and then washed with water three times. After washing, the collected polymer solid was dried in a vacuum dryer at 90 ° C. for 72 hours to obtain polyethersulfone resin A. The resulting powder was measured by infrared absorption spectrum by KBr method, around ^-1 peak 1578cm due to the structure of ^{polyethersulfone, 1484cm -1, 1238cm -1, 1149cm} -1, 1103cm around ^-1 Detected. The weight average molecular weight (Mw) of the polymer thus obtained was calculated to be 92000. The terminal hydroxyl group content was 40 mol%. Moreover, when the glass transition temperature was measured using DSC method using the obtained powder, it was 230 degreeC.

Synthesis Example 2: Synthesis of polyethersulfone resin B (depolymerization method)
In a 500 mL three-necked flask equipped with a nitrogen introduction tube, a stirring rod, and a thermometer, 24.6 g (0.11 mol, manufactured by Sumitomo Chemical Co., Ltd.) and 4,4′- Dihydroxydiphenyl sulfone 0.41 g (0.0016 mol, manufactured by Wako Pure Chemical Industries, Ltd.) and anhydrous potassium carbonate 1.47 g (0.01 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) are dissolved in 180 g of NMP and 20 g of toluene. And the temperature of the solution was reacted at 150 ° C. for 5 hours. Thereafter, cooling was performed, and when the temperature of the solution decreased to room temperature, the solution was poured into 3 L of methanol to obtain a white polymer solid. The polymer solid was collected by filtration, further washed with methanol twice, and then washed with water three times. After washing, the collected polymer solid was dried in a vacuum dryer at 90 ° C. for 72 hours to obtain polyethersulfone resin B. The resulting powder was measured by infrared absorption spectrum by KBr method, around ^-1 peak 1578cm due to the structure of ^{polyethersulfone, 1484cm -1, 1238cm -1, 1149cm} -1, 1103cm around ^-1 Detected. The weight average molecular weight (Mw) of the polymer thus obtained was calculated to be 33000. The terminal hydroxyl group content was 50 mol%. Moreover, it was 220 degreeC when the glass transition temperature was measured using DSC method using the obtained polymer powder.

Synthesis Example 3: Synthesis of polyethersulfone resin C (depolymerization method)
Sumika Excel 5300P 20 g (0.086 mol, manufactured by Sumitomo Chemical Co., Ltd.) and 4,4′-dihydroxydiphenyl were added to a 500 mL three-necked flask equipped with a nitrogen inlet tube, a stirring rod, and a thermometer under a dry nitrogen stream. 1.13 g of sulfone (0.0045 mol, manufactured by Wako Pure Chemical Industries, Ltd.) and 0.251 g of anhydrous potassium carbonate (0.0086 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 180 g of NMP and 20 g of toluene, The temperature of the solution was reacted at 150 ° C. for 5 hours. Thereafter, cooling was performed, and when the temperature of the solution decreased to room temperature, the solution was poured into 3 L of methanol to obtain a white polymer solid. The polymer solid was collected by filtration, further washed with methanol twice, and then washed with water three times. After washing, the collected polymer solid was dried in a 90 ° C. vacuum dryer for 72 hours to obtain polyethersulfone resin C. The resulting powder was measured by infrared absorption spectrum by KBr method, around ^-1 peak 1578cm due to the structure of ^{polyethersulfone, 1484cm -1, 1238cm -1, 1149cm} -1, 1103cm around ^-1 Detected. The weight average molecular weight (Mw) of the polymer thus obtained was calculated to be 20100. The terminal hydroxyl group content was 50 mol%. Moreover, it was 210 degreeC when the glass transition temperature was measured using DSC method using the obtained polymer powder.

Synthesis Example 4: Synthesis of polyethersulfone resin D (depolymerization method)
Sumika Excel 4800P20g (0.086 mol, manufactured by Sumitomo Chemical Co., Ltd.) and 4,4'-dihydroxydiphenyl in a 500 mL three-necked flask equipped with a nitrogen inlet tube, a stir bar, and a thermometer under a dry nitrogen stream 5.38 g of sulfone (0.00215 mol, manufactured by Wako Pure Chemical Industries, Ltd.) and 1.19 g of anhydrous potassium carbonate (0.0086 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 180 g of NMP and 20 g of toluene, The temperature of the solution was reacted at 150 ° C. for 5 hours. Thereafter, cooling was performed, and when the temperature of the solution decreased to room temperature, the solution was poured into 3 L of methanol to obtain a white polymer solid. The polymer solid was collected by filtration, further washed with methanol twice, and then washed with water three times. After washing, the collected polymer solid was dried in a vacuum dryer at 90 ° C. for 72 hours to obtain polyethersulfone resin D. The resulting powder was measured by infrared absorption spectrum by KBr method, around ^-1 peak 1578cm due to the structure of ^{polyethersulfone, 1484cm -1, 1238cm -1, 1149cm} -1, 1103cm around ^-1 Detected. The weight average molecular weight (Mw) of the polymer thus obtained was calculated to be 7968. The terminal hydroxyl group content was 50 mol%. Moreover, it was 210 degreeC when the glass transition temperature was measured using DSC method using the obtained polymer powder.

Synthesis Example 5 Synthesis of Modified Polypropylene Glycol Compound 110 g (0.1 mol) of a diol type polypropylene glycol having a number average molecular weight of 1100 was placed in a 1 L separable flask equipped with a condenser and a stirrer and stirred at 80 ° C. in a nitrogen atmosphere. Then, 0.67 g of dibutyltin laurate was added dropwise. Thereafter, 23.8 g (0.2 mol) of phenyl isocyanate was added and stirred at 80 ° C. for 90 minutes to obtain polypropylene glycol end-capped with phenyl isocyanate. The structure of the synthesized liquid terminal phenyl isocyanate-modified polypropylene glycol was confirmed by FT-IR, ¹ H-NMR and GPC. The number average molecular weight was 1340.

Synthesis Example 6 Synthesis of Polyimide Compound In a 1 L separable flask equipped with a cooling tube and a stirrer, 411.9 g (1.40 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, bis (3 -Carboxy-4-aminophenyl) methane 71.58 g (0.25 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 186 g (0.75 mol) triethylene glycol dimethyl ether (trade name, Maruzen Petroleum) A polyimide solution (solid content concentration 56.5%) was obtained by stirring in a solvent at a temperature of 160 ° C. for 6 hours. After stirring, the solution was cooled to room temperature, and then the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried at 80 ° C. for 20 hours using a vacuum dryer to obtain a white powdered polyimide compound.

The raw materials used in each example and comparative example are shown below.
Polyethersulfone resin:
Sumika Excel 5003P (trade name, manufactured by Sumitomo Chemical Co., Ltd .: weight average molecular weight 67250, terminal phenolic hydroxyl group content 46 mol%, glass transition temperature 230 ° C.)
Ultrazone E2020P (trade name, manufactured by Sumitomo Chemical Co., Ltd .: weight average molecular weight 56000, terminal phenolic hydroxyl group content 44 mol%, glass transition temperature 225 ° C.)
Sumika Excel 4800P (trade name, manufactured by Sumitomo Chemical Co., Ltd .: weight average molecular weight 66700, no terminal phenolic hydroxyl group, glass transition temperature 225 ° C.)
Sumika Excel 3600P (trade name, manufactured by Sumitomo Chemical Co., Ltd .: weight average molecular weight 46000, no terminal phenolic hydroxyl group, glass transition temperature 225 ° C.)
Epoxy compound represented by general formula (1):
GAN (trade name, manufactured by Nippon Kayaku Co., Ltd.): Diglycidylaniline)
GOT (trade name, manufactured by Nippon Kayaku Co., Ltd.): Diglycidyl orthotoluidine)
Epoxy compound represented by general formula (2):
Triglycidyl p-aminophenol = “jER” 630 (trade name, manufactured by Japan Epoxy Resin Co., Ltd .: p-aminophenol triglycidyl epoxy compound)
Triglycidyl p-aminocresol = p-aminocresol triglycidyl epoxy compound Epoxy compound represented by formula (3):
TGDDM = “jER” 604 (trade name, manufactured by Japan Epoxy Resin Co., Ltd .: diaminodiphenylmethane type epoxy compound)
TGDDS: Epoxy compounds other than diaminodiphenyl sulfone type epoxy compounds (1) to (3):
“JER” 807 (trade name, manufactured by Japan Epoxy Resin Co., Ltd .: bisphenol F type liquid epoxy resin)
YED216M (trade name, manufactured by Japan Epoxy Resin Co., Ltd.): 1,6-hexanediol diglycidyl ether)
Epoxy compound A = “Epiclon” 850S (trade name, manufactured by Dainippon Ink & Chemicals, Inc .: bisphenol A type liquid epoxy resin)
Epoxy compound B = 2 epoxy compound derived from polycondensate of 2-t-butyl-5-methylphenol and 4-hydroxybenzaldehyde (synthesized according to Japanese Patent Publication No. 7-121979, Reference Example 1)
Epoxy compound C = “jER” 157S70 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.): bisphenol A type novolac epoxy compound)
Epoxy compound D == “jER” 1032H60 (trade name, manufactured by Japan Epoxy Resin Co., Ltd .: trishydroxyphenylmethane type epoxy compound)
Epoxy compound having an SP value of 2.00 × 10 ^{4 to} 2.60 × 10 ⁴ (J / m ³ ) ^1/2 :
“JER” 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.): epoxy equivalent 187 g / eq, SP value = 12.31 (cal / cm ³ ) ^1/2 = 2.52 × 10 ⁴ (J / m ^{3 1/2}
“JER” 807 (trade name, manufactured by Japan Epoxy Resins Co., Ltd.): Epoxy equivalent 169 g / eq, SP value = 11.47 (cal / cm ³ ) ^1/2 = 2.35 × 10 ⁴ (J / m ^{3 1/2}
N660 (trade name, manufactured by DIC Corporation: cresol novolac solid epoxy resin: epoxy equivalent 206 g / eq, SP value = 10.11 (cal / cm ³ ) ^1/2 = 2.07 × 10 ⁴ (J / m ) ^1/2 )
EXA4710 (trade name, manufactured by DIC Corporation: naphthalene type solid epoxy resin: epoxy equivalent 170 g / eq, SP value = 10.07 (cal / cm ³ ) ^1/2 = 2.06 × 10 ⁴ (J / m) ^1/2 ))
Epoxy compound having an SP value of 1.60 × 10 ^{4 to} 1.80 × 10 ⁴ (J / m ³ ) ^1/2 :
Epolite 400E (trade name, manufactured by Kyoeisha Chemical Co., Ltd.): polyethylene glycol diglycidyl ether, epoxy equivalent of 264 to 290 g / eq, SP value = 8.58 (cal / cm ³ ) ^1/2 = 1.76 × 10 ⁴ (J / m ³ ) ^1/2
YED216M (trade name, manufactured by Japan Epoxy Resin Co., Ltd.): 1,6-hexanediol diglycidyl ether, epoxy equivalent 148 g / eq, SP value = 8.25 (cal / cm ³ ) ^1/2 = 1.69 × 10 ⁴ (J / m ³ ) ^1/2
Oxetane compounds:
POX (abbreviation) = OXT-211 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.): 3-ethyl-3- (phenoxymethyl) oxetane OXIPA (abbreviation) = “Ethanacol” OXIPA (trade name, Ube Industries, Ltd.) Made)
Curing agents and curing accelerators:
Curing agent A: aromatic diamine (one-to-one mixture of 4,4′-diaminodiphenylsulfone and 3,3′-diaminodiphenylsulfone (manufactured by Wako Pure Chemical Industries, Ltd.))
Curing agent A-2: APB-N: aromatic diamine: m-bis (m-aminophenoxy) benzene (manufactured by Mitsui Chemicals)
Curing agent A-3: TPE-R: aromatic diamine: m-bis (p-aminophenoxy) benzene (manufactured by Wakayama Seika Kogyo Co., Ltd.)
Curing agent A-4: APB-5: Aromatic diamine: Bis (m- (m-aminophenoxy) phenoxy) benzene (Mitsui Chemicals, Inc.))
Curing accelerator B: 3,4-dichlorophenyl-N, N-dimethylurea (manufactured by Tokyo Chemical Industry Co., Ltd.)
Curing agent C: 2E4MZ (2-ethyl-4-methylimidazole) (trade name, manufactured by Shikoku Chemicals Co., Ltd., water-insoluble)
Curing agent D: aromatic diamine = Kayahard AA (trade name, 3,3′-diethyl-4,4′-diaminodiphenylmethane, manufactured by Nippon Kayaku Co., Ltd.)
Thermoplastic resins other than polyethersulfone:
Maleimide compound: a compound having a polytetramethylene glycol linking chain of b = 2 to 3 represented by the following general formula (8) Modified polypropylene glycol compound: compound obtained in Synthesis Example 5 Polyimide compound: obtained in Synthesis Example 6 Polyimide compound inorganic fine particles and organic fine particles obtained:
Spherical silica fine particles A: Admafine GRJ (trade name, manufactured by Admatechs Co., Ltd .: surface modified silica fine particles, surface modified particles, average particle size 0.5 μm)
Spherical styrene fine particles A: Ganzpearl (trade name, manufactured by Ganz Kasei Co., Ltd .: polystyrene organic fine particles, average particle size 2.5 μm)
solvent:
Solvent A: NMP (abbreviation) =: N-methylpyrrolidone (trade name, manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 202-204 ° C.)
Solvent B: DMF (abbreviation) =: N, N-dimethylformamide (trade name, manufactured by Wako Pure Chemical Industries, Ltd., boiling point 153 ° C.)
Solvent C: Triglyme (abbreviation) =: Triethylene glycol dimethyl ether (trade name, manufactured by Maruzen Petrochemical Co., Ltd., boiling point 216 ° C.).

Example 1
The polyethersulfone resin A 10 g, GOT 12 g, triglycidyl p-aminophenol 10 g, and TGDDM 10 g obtained in Synthesis Example 1 were stirred and mixed at 25 ° C. for 60 minutes using a planetary stirring and degassing machine (Mazerustar (manufactured by Kurabo Industries)). Then, 17 g of the curing agent A was added, and the mixture was further stirred and mixed for 30 minutes, and finally defoamed to obtain an underfill agent A-1. The obtained underfill agent A-1 was measured and evaluated by the above methods for the glass transition temperature, viscosity characteristics, solubility, storage stability, curing start temperature, fracture toughness value, and presence of voids.

Example 2
Underfill agent B-1 was obtained in the same manner as in Example 1 except that Sumika Excel 5003P10 g was used instead of the polyethersulfone resin A10 g, and measurement and evaluation were performed in the same manner as in Example 1.

Example 3
Underfill agent C-1 was obtained in the same manner as in Example 1 except that Ultra Zone E2020P10 g was used in place of the polyethersulfone resin A10 g, and measurement and evaluation were performed in the same manner as in Example 1.

Example 4
Underfill agent D-1 was obtained in the same manner as in Example 1 except that the polyethersulfone resin B10g obtained in Synthesis Example 2 was used in place of the polyethersulfone resin A10g. evaluated.

Example 5
Underfill agent E-1 was obtained in the same manner as in Example 1 except that Sumika Excel 4800P10 g was used instead of 10 g of the polyethersulfone resin A, and measurement and evaluation were performed in the same manner as in Example 1.

Example 6
Underfill agent F-1 was obtained in the same manner as in Example 1 except that Sumika Excel 3600P10 g was used instead of the polyethersulfone resin A10 g, and measurement and evaluation were performed in the same manner as in Example 1.

Example 7
Sumika Excel 5003P10g, GAN12g, triglycidyl p-aminophenol 10g, and TGDDM 10g were mixed by stirring for 60 minutes at 25 ° C using a planetary stirring deaerator (Mazerustar (manufactured by Kurabo Industries)), and then 17g of curing agent A was added. The mixture was further stirred for 30 minutes and mixed, and finally defoamed to obtain an underfill agent G-1. The glass transition temperature, viscosity characteristics, solubility, storage stability, curing start temperature, fracture toughness value, presence / absence of voids, and average thermal expansion coefficient of the obtained underfill agent G-1 were measured and evaluated by the above methods. The measurement temperature ranges of the average thermal linear expansion coefficient were T ₁ = 25 ° C. and T ₂ = 170 ° C.

Example 8
Underfill agent G-2 was obtained in the same manner as in Example 7 except that Sumika Excel 5003P10 g was replaced with 25 g. The obtained underfill agent G-2 was measured and evaluated by the above-mentioned methods for glass transition temperature, viscosity characteristics, solubility, storage stability, curing start temperature, fracture toughness value, and presence of voids.

Example 9
Underfill agent G-3 was obtained in the same manner as in Example 7 except that 5 g of Sumika Excel 5003P was replaced with 5 g, and measured and evaluated in the same manner as in Example 8.

Example 10
Underfill agent G-4 was obtained in the same manner as in Example 7 except that 10 g of triglycidyl p-aminocresol was used instead of 10 g of triglycidyl p-aminophenol, and measurement and evaluation were performed in the same manner as in Example 8.

Example 11
Underfill agent G-5 was obtained in the same manner as in Example 7 except that TGDDS 10 g was used instead of TGDDM 10 g, and measurement and evaluation were performed in the same manner as in Example 8.

Example 12
Sumika Excel 5003P 10 g, GAN 12 g, triglycidyl p-aminophenol 10 g, and TGDDM 10 g were mixed by stirring at 25 ° C. for 60 minutes using a planetary stirring deaerator (Mazerustar (manufactured by Kurabo Industries)), and then 17 g of curing agent A, 1 g of curing accelerator B was added, and the mixture was further stirred and mixed for 30 minutes. Finally, defoaming was performed to obtain an underfill agent G-6, which was measured and evaluated in the same manner as in Example 8.

Example 13
Sumika Excel 5003P 10 g, GAN 12 g, triglycidyl p-aminophenol 10 g, and TGDDM 10 g were mixed by stirring at 25 ° C. for 60 minutes using a planetary stirring deaerator (Mazerustar (manufactured by Kurabo Industries)), and then spherical silica fine particles A were mixed. 6 g was added and mixed by stirring for 30 minutes, and then kneaded with three rolls. Thereafter, 17 g of curing agent A was added, and the mixture was further stirred and mixed for 30 minutes. Finally, defoaming was performed to obtain an underfill agent G-7, which was measured and evaluated in the same manner as in Example 7.

Example 14
Underfill agent G-8 was obtained in the same manner as in Example 13 except that the spherical silica fine particles A6g were replaced with 25 g, and measured and evaluated in the same manner as in Example 7.

Example 15
Underfill agent G-9 was obtained in the same manner as in Example 13 except that 6 g of spherical silica fine particles A was replaced with 60 g, and measured and evaluated in the same manner as in Example 7.

Example 16
Underfill agent G-10 was obtained in the same manner as in Example 13 except that the spherical silica fine particles A6g were replaced with 140 g, and measured and evaluated in the same manner as in Example 7.

Example 17
Sumika Excel 5003P 10 g, GAN 12 g, triglycidyl p-aminophenol 10 g, and TGDDM 10 g were mixed by stirring at 25 ° C. for 60 minutes using a planetary stirring and degassing machine (Mazerustar (manufactured by Kurabo Industries)). 25 g was added and mixed by stirring for 30 minutes, and then kneaded with three rolls. Thereafter, 17 g of curing agent A was added, and the mixture was further stirred and mixed for 30 minutes. Finally, defoaming was performed to obtain an underfill agent G-11, which was measured and evaluated in the same manner as in Example 7.

Example 18
Sumika Excel 5003P 10 g, GAN 12 g, triglycidyl p-aminophenol 10 g, and TGDDM 10 g were mixed by stirring for 60 minutes at 25 ° C. using a planetary stirring deaerator (Mazerustar (manufactured by Kurabo Industries)). 5 g was added, and the mixture was further stirred for 30 minutes to be mixed, and finally defoamed to obtain an underfill agent G-12, which was measured and evaluated in the same manner as in Example 8.

Example 19
Sumika Excel 5003P 10 g, GAN 12 g, triglycidyl p-aminophenol 10 g, TGDDM 10 g, and OXIPA 5 g were mixed by stirring for 60 minutes at 25 ° C. using a planetary stirring deaerator (Mazerustar (manufactured by Kurabo Industries)), and then curing agent A 17 g was added, and the mixture was further stirred and mixed for 30 minutes. Finally, defoaming was performed to obtain an underfill agent G-13, which was measured and evaluated in the same manner as in Example 8.

Example 20
Sumika Excel 5003P 10 g, GAN 12 g, triglycidyl p-aminophenol 10 g, TGDDM 10 g, and POX 5 g were mixed by stirring at 25 ° C. for 60 minutes using a planetary stirring deaerator (Mazerustar (manufactured by Kurabo Industries)), and then curing agent A Was added and stirred for another 30 minutes. Finally, defoaming was performed to obtain an underfill agent G-14, which was measured and evaluated in the same manner as in Example 8.

Example 21
Sumika Excel 5003P 10 g, GAN 12 g, triglycidyl p-aminophenol 10 g, TGDDM 10 g, and “jER” 807 10 g were stirred and mixed at 25 ° C. for 60 minutes using a planetary stirring deaerator (Mazerustar (manufactured by Kurabo Industries)). Then, 17 g of curing agent A was added, and the mixture was further stirred and mixed for 30 minutes. Finally, defoaming was performed to obtain an underfill agent G-15, which was measured and evaluated in the same manner as in Example 8.

Example 22
Sumika Excel 5003P 10 g, GAN 12 g, triglycidyl p-aminophenol 10 g, TGDDM 10 g, and YED216M5 g were stirred and mixed at 25 ° C. for 60 minutes using a planetary stirring deaerator (Mazerustar (manufactured by Kurabo Industries)), then curing agent A 17 g was added, and the mixture was further stirred and mixed for 30 minutes. Finally, defoaming was performed to obtain an underfill agent G-16, which was measured and evaluated in the same manner as in Example 8.

Example 23
Sumika Excel 5003P 10 g, “jER” 828 10 g, and YED216M 10 g were mixed by stirring for 60 minutes at 25 ° C. using a planetary stirring deaerator (Mazerustar (manufactured by Kurabo Industries)), and then 8.85 g of curing agent A-2. The mixture was further stirred for 30 minutes and mixed, and finally defoamed to obtain an underfill agent G-17, which was measured and evaluated in the same manner as in Example 8.

Example 24
Underfill agent G-18 was obtained in the same manner as in Example 23, except that 10 g of “jER” 807 was used instead of 10 g of “jER” 828, and curing agent A-2 was changed from 8.85 g to 9.26 g. It was. The underfill agent G-18 obtained has a glass transition temperature, viscosity characteristics, solubility, storage stability, curing start temperature, fracture toughness value, presence of voids, average coefficient of thermal expansion (T ₁ = 25 ° C., T ₂ = 60 ° C.) was measured and evaluated by the above method.

Example 25
10 g of N660 and 10 g of YED216M were put into a 500 mL three-necked flask equipped with a nitrogen introducing tube, a stirring rod, and a thermometer, and dissolved by stirring at 70 ° C. for 1 hour under a dry nitrogen stream. Further, 10 g of Sumika Excel 5003P was added, and after stirring and mixing at 25 ° C. for 30 minutes using a planetary stirring and defoaming machine (Mazerustar (manufactured by Kurabo Industries)), 8.48 g of curing agent A-2 was added. The mixture was stirred for 30 minutes and finally defoamed to obtain an underfill agent G-19, which was measured and evaluated in the same manner as in Example 8.

Example 26
10 g of EXA4710 and 10 g of YED216M were put into a 500 mL three-necked flask equipped with a nitrogen introduction tube, a stirring rod, and a thermometer, and dissolved by stirring at 80 ° C. for 1 hour in a dry nitrogen stream. Further, 10 g of Sumika Excel 5003P was added, and after stirring and mixing for 30 minutes at 25 ° C. using a planetary stirring and defoaming machine (Mazerustar (manufactured by Kurabo Industries)), 9.24 g of curing agent A-2 was added, and The mixture was stirred for 30 minutes and finally defoamed to obtain an underfill agent G-20, which was measured and evaluated in the same manner as in Example 8.

Example 27
Underfill agent G-21 was obtained in the same manner as in Example 24 except that 10 g of Epolite 400E was used instead of 10 g of YED216M and the curing agent A-2 was changed from 9.26 g to 6.96 g. Measured and evaluated.

Example 28
Underfill agent G-22 was obtained in the same manner as in Example 24 except that 9.26 g of curing agent A-3 was used instead of 9.26 g of curing agent A-2, and measurement and evaluation were performed in the same manner as in Example 8. did.

Example 29
Underfill agent G-23 was obtained in the same manner as in Example 24 except that 15.10 g of curing agent A-4 was used instead of 9.26 g of curing agent A-2. Measurement and evaluation were performed in the same manner as in Example 8. did.

Example 30
Sumika Excel 5003P 10 g, “jER” 807 10 g, and YED216M 10 g were stirred and mixed at 25 ° C. for 60 minutes using a planetary stirring deaerator (Mazerustar (manufactured by Kurabo Industries)), and then 4.36 g of spherical silica fine particles A were added. The mixture was stirred for 30 minutes and mixed, and then kneaded with three rolls. 9.26 g of curing agent A-2 was added, and the mixture was further stirred for 30 minutes to be mixed. Finally, defoaming was performed to obtain an underfill agent G-24, which was measured and evaluated in the same manner as in Example 24.

Example 31
Underfill agent G-25 was obtained in the same manner as in Example 24 except that 7.86 g of curing agent A was used instead of 9.26 g of curing agent A-2, and measurement and evaluation were performed in the same manner as in Example 8.

Comparative Example 1
Underfill agent G′-1 was obtained in the same manner as in Example 15 except that 0.5 g of solvent A was replaced with 40 g, and measured and evaluated in the same manner as in Example 8.

Comparative Example 2
Underfill agent G′-2 was obtained in the same manner as in Example 7 except that the epoxy compound was not used, but it was in a solid powder state.

Comparative Example 3
Underfill agent G′-3 was obtained in the same manner as in Example 7 except that Sumika Excel 5003P was not used, and was measured and evaluated in the same manner as in Example 8.

Comparative Example 4
Underfill agent G′-4 was obtained in the same manner as in Example 7 except that polyethersulfone resin C was used instead of Sumika Excel 5003P10 g, and measurement and evaluation were performed in the same manner as in Example 8.

Comparative Example 5
Underfill agent G′-5 was obtained in the same manner as in Example 7 except that polyethersulfone resin D was used instead of Sumika Excel 5003P10 g, and measurement and evaluation were performed in the same manner as in Example 8.

Comparative Example 6
10 g of epoxy resin A, 10 g of maleimide compound, and 12 g of spherical silica fine particles A were mixed by stirring for 60 minutes at 25 ° C. using a planetary stirring deaerator (Mazerustar (manufactured by Kurabo Industries)), and then kneaded with three rolls. Thereafter, 0.2 g of curing agent C was added, and the mixture was further stirred and mixed for 30 minutes. Finally, defoaming was performed to obtain underfill G′-6, which was measured and evaluated in the same manner as in Example 7.

Comparative Example 7
25 g of triglycidyl p-aminophenol, 25 g of YED216M, 25 g of epoxy resin A, 13 g of modified polypropylene glycol compound, and A154 g of spherical silica fine particles were stirred and mixed at 25 ° C. for 60 minutes using a planetary stirring deaerator (Mazerustar (Kurabo)). Then, the mixture was kneaded with three rolls. Thereafter, 48 g of curing agent D was added, and the mixture was further stirred and mixed for 30 minutes. Finally, defoaming was performed to obtain underfill G′-7, which was measured and evaluated in the same manner as in Example 7.

Comparative Example 8
Sumika Excel 5003P 30 g, Epoxy resin B 47 g, Epoxy resin C 23 g, Epoxy resin D 23 g, and spherical silica fine particles A 25 g were stirred and mixed at 25 ° C. for 60 minutes using a planetary stirring deaerator (Mazerustar (manufactured by Kurabo Industries)). It knead | mixed with 3 rolls. Thereafter, 0.1 g of curing agent C was added, and the mixture was further stirred for 30 minutes to be mixed. Finally, 100 g of solvent B was added, and the mixture was further stirred and mixed for 30 minutes, defoamed to obtain underfill G′-8, and measured and evaluated in the same manner as in Example 7.

Comparative Example 9
After 15 g of epoxy resin D and 57 g of polyimide compound were mixed by stirring for 60 minutes at 25 ° C. using a planetary stirring and defoaming machine (Mazerustar (manufactured by Kurabo Industries)), 0.3 g of curing agent C was added, and another 30 minutes Stir and mix. Finally, 44 g of solvent C was added, and the mixture was further stirred and mixed for 30 minutes, defoamed to obtain underfill G′-9, and measured and evaluated in the same manner as in Example 8.

  The composition of each Example and Comparative Example is shown in Tables 1-4, and the evaluation results are shown in Tables 5-7.

1: DSC curve 2: extension line of L ₁ 3: extension line of L ₂ 4: intersection point P: peak L ₁ : straight line portion L ₂ : straight line portion recognized until reaching the peak after rising

Claims (9)

(A) a weight average molecular weight of 30,000 or more polyether sulfone resin, (b) containing epoxy compound state, and are 1 wt% or less content of (c) solvents, (b) epoxy compounds, SP value Is an aliphatic glycidyl ether type epoxy compound having an SP value of 2.00 × 10 ^{4 to} 2.60 × 10 ^{4, which} is 1.60 × 10 ^{4 to} 1.80 × 10 ⁴ (J / m ³ ) ^1/2. (J / m ³ ) An underfill agent characterized by containing one or more epoxy compounds each being ^1/2 . 2. The underfill agent according to claim 1, comprising (a) 5 to 40% by weight of a polyethersulfone resin having a weight average molecular weight of 30,000 or more. The underfill agent according to claim 1 or 2, wherein the polyether sulfone resin (a) having a weight average molecular weight of 30,000 or more has a phenolic hydroxyl group. The underlayer according to any one of claims 1 to 3 , further comprising (d) at least one inorganic fine particle selected from the group consisting of silica, titania, zirconia, silicon nitride, alumina, ceria, talc and calcium carbonate. Fill agent. Further, (e) polyimide, polyamide, polyamideimide, polystyrene, polyacrylonitrile, polyphenylene ether, claim 1-4, wherein any one, characterized in that it contains at least one organic fine particles selected from the group consisting of polyesters and polycarbonates Underfill agent. Further, a curing agent is contained, and the content of the curing agent is 0.1 to 60 parts by weight with respect to 100 parts by weight of the total amount of the polyethersulfone resin as the component (a) and the epoxy compound (b). The underfill agent according to any one of claims 1 to 5 . In the viscoelasticity-temperature curve obtained by dynamic viscoelasticity measurement (temperature increase rate 2 ° C./min), the minimum viscosity value η ^* is 1.0 × 10 ² Pa · s or less, and the minimum viscosity value is The underfill agent according to any one of claims 1 to 6 , wherein the temperature shown is 70 to 120 ° C. The underfill agent according to any one of claims 1 to 7 , wherein the fracture toughness value K1c is 1.5 MPa · m ^1/2 or more. A semiconductor device using an underfill agent in accordance with claim 1-8.

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