JP5233091B2 - Liquid resin composition and semiconductor device produced using liquid resin composition - Google Patents

Description

  The present invention relates to a liquid resin composition and a semiconductor device manufactured using the liquid resin composition.

In recent years, with the reduction in size, weight, and performance of electronic devices, the shift to area-mounted semiconductor devices has been spurred. Typical area-mounting semiconductor devices include BGA (ball grid array) or CSP (chip scale package) pursuing further miniaturization. These correspond to the demands for higher pin count and higher speed, which are approaching the limit in the conventional surface mount semiconductor devices represented by QFP, SOP, and the like. The structure is a hard circuit board represented by BT resin / copper foil circuit board (bismaleimide / triazine resin / glass cloth board) or an organic board such as a flexible circuit board represented by polyimide resin film / copper foil circuit board. A semiconductor element is mounted on one side, and only the semiconductor element mounting surface, that is, one side of the substrate is molded and sealed with an epoxy resin composition or the like. In addition, solder balls are two-dimensionally formed in parallel on the surface opposite to the semiconductor element mounting surface of the substrate, and are joined to the circuit substrate on which the semiconductor device is mounted. These area-mounted semiconductor devices have a single-side sealing configuration in which only the semiconductor element mounting surface of the substrate is sealed with an epoxy resin composition and the solder ball forming surface side is not sealed. Members having an expansion coefficient are present in layers, and thermal expansion and contraction of each member accompanying a temperature change are expressed as stress inside the semiconductor device, often causing peeling and cracking. (For example, refer to Patent Document 1.)
In addition, solder balls have been replaced from tin-lead solder to lead-free solder as part of the elimination of lead from semiconductor products for environmental reasons. Since lead-free solder has a higher melting point than tin-lead solder, it is necessary to increase the reflow temperature when mounting a semiconductor device on a circuit board such as a motherboard when mounting solder balls on an organic substrate. The problem is getting more pronounced.
The liquid resin composition (die attach material) used when adhering a semiconductor element to an organic substrate also has problems with peeling and cracks that occur during reflow processing, and can withstand stress during high-temperature reflow. A high adhesion force to the device and a low elastic modulus characteristic are required, and a substance that does not generate a void after curing, which is a cause of peeling, is required, but none is satisfied.
JP 2006-188622 A

  The present invention provides a liquid resin composition that exhibits good adhesion and low elastic modulus, and does not generate voids upon curing, and particularly reliability such as solder crack resistance when the present invention is used as a die attach material for semiconductors. It is to provide an excellent semiconductor device.

Such an object is achieved by the present invention described in the following [1] to [5].
[1] It comprises (A) a filler, (B) a thermosetting resin, (C) a curing catalyst, and (D) an additive, and the thermosetting resin (B) has the same functional group in one molecule. It consists of only two compounds, a compound (B1) having two glycidyl groups in one molecule, a compound (B2) having two (meth) acryloyl groups in one molecule, and a maleimide group in one molecule. A liquid resin composition comprising two compounds (B3).
[2] The liquid resin composition according to [1], wherein the curing catalyst (C) includes an organic peroxide (C1).
[3] The liquid resin composition according to [2], wherein the organic peroxide (C1) includes a compound having an exothermic start temperature in a rapid heating test of 40 ° C. or higher and 100 ° C. or lower.
[4] The liquid resin composition according to any one of [1] to [3], wherein the liquid resin composition is for bonding a semiconductor element and an organic substrate.
[5] A semiconductor device manufactured using the liquid resin composition according to any one of [1] to [4] as a die attach material.

  The liquid resin composition of the present invention exhibits a good adhesive force and a low elastic modulus and a good low-stress property. Since no voids are generated during curing, the present invention can be used by using the present invention as a die attach material. It is possible to provide a highly reliable semiconductor device that does not have a high reliability.

The present invention comprises a filler, a thermosetting resin, a curing catalyst, and an additive, and the thermosetting resin is composed of only a compound having two functional groups of the same type in one molecule and has at least three different functional groups. It is a liquid resin composition containing a compound, and exhibits a good adhesive force, a low elastic modulus, a good low stress property and no voids, so that it can be used as a liquid resin composition for adhering semiconductor elements. It is possible to provide an unprecedented highly reliable semiconductor device.
Hereinafter, the present invention will be described in detail.

  In the present invention, as filler (A), silver powder, gold powder, copper powder, aluminum powder, nickel powder, metal powder such as palladium powder, ceramic powder such as alumina powder, titania powder, aluminum nitride powder, boron nitride powder, Polymer powders such as polyethylene powder, polyacrylic acid ester powder, polytetrafluoroethylene powder, polyamide powder, polyurethane powder, and polysiloxane powder can be used. Since the liquid resin composition may be ejected using a nozzle, the average particle diameter of the filler is preferably 30 μm or less in order to prevent clogging of the nozzle, and it is preferable that there are few ionic impurities such as sodium and chlorine. In particular, silver powder is preferably used when electrical conductivity and thermal conductivity are required. If it is the silver powder currently marketed for electronic materials normally, reduced powder, atomized powder, etc. can be obtained, and as an average particle diameter, an average particle diameter is 1 micrometer or more and 30 micrometers or less. Below this, the viscosity of the liquid resin composition becomes too high, and above this can cause nozzle clogging during dispensing as described above, and silver powder other than for electronic materials may have a large amount of ionic impurities. So be careful. The shape is not particularly limited, such as flakes and spheres, but preferably flakes are used, and are usually contained in the liquid resin composition in an amount of 65% by weight to 95% by weight. This is because when the proportion of silver powder is less than this, the conductivity deteriorates, and when it is more than this, the viscosity of the liquid resin composition becomes too high.

The thermosetting resin (B) to be used in the present invention is a polymer that is heated together with the curing catalyst (C) to increase the molecular weight by heating, and 2 functional groups of the same type are contained in one molecule. It is composed of at least three kinds of compounds which are composed of only one compound and have different functional groups. Here, a compound having two functional groups of the same type in one molecule means that if the compound is designed to have two functional groups at the time of compound preparation, a component having one function or more than three functions as impurities other than the target product. It may be included, and there is no problem unless a component having a monofunctional or trifunctional or higher function is intentionally added or a condition for generating a monofunctional or trifunctional or higher component is intentionally selected. Make it not exist. Here, the number of functional groups contained in one molecule is limited to two. However, when the number of functional groups is smaller than this, the cohesive force of the cured product is lowered and does not exhibit good adhesive properties. If the amount is larger than this, the crosslinking density becomes high, and as a result, the elastic modulus may be too high. Preferred functional groups contained in one molecule are glycidyl groups,
Carboxy group, hydroxyl group, (meth) acryloyl group, (meth) allyl group, vinyl group, maleimide group and the like, and more preferably used functional groups are glycidyl group, hydroxyl group, (meth) acryloyl group, maleimide group, The thermosetting resin (B) is a compound (B1) having two glycidyl groups in one molecule, a compound (B2) having two (meth) acryloyl groups in one molecule, and two maleimide groups in one molecule. It is particularly preferred that the compound (B3) it has is included.

In the present invention, a preferable compound (B1) is not particularly limited as long as it has two glycidyl groups in one molecule. From the viewpoint of reactivity, the glycidyl group is bonded to an aromatic carbon atom via an oxygen atom. preferable. In addition, the number of functional groups contained in one molecule is limited to two. This is because when the number of functional groups contained in one molecule is one, the cohesive force of the cured product is reduced, and as a result This is because the adhesive strength is lowered, and in the case of 3 or more, the crosslink density of the cured product is increased, and as a result, the cured product has a high elastic modulus and causes a decrease in stress absorption characteristics. Preferred compounds (B1) include diglycidyl etherified compounds, naphthalenediol, anthracenediol, or diglycidyl derivatives of these compounds having two phenolic hydroxyl groups in one molecule such as bisphenol F, bisphenol A, biphenol or derivatives thereof. Etherified compounds can be used, and these can be used alone or in combination, but can be used in combination with an aliphatic diglycidyl compound, but aliphatic diglycidyl compounds are inferior in reactivity and are not preferred for use alone. Examples of aliphatic glycidyl compounds that can be used in combination include hydrogenated bisphenol F, hydrogenated bisphenol A, hydrogenated biphenol or derivatives thereof, cyclohexanedimethanol, cyclohexanediethanol, and other diglycidyl ether compounds of dialkyl alcohols of cyclohexane. Can be mentioned. Other preferred compounds (B1) include diglycidyl ether compounds in which a polyalkylene oxide group is introduced into the molecular chain for the purpose of lowering the elastic modulus of the cured product. Here, the diglycidyl ether compound into which the polyalkylene oxide group is introduced is preferably a glycidyloxyphenyl group in which the glycidyl ether group is bonded to an aromatic carbon atom from the viewpoint of reactivity. That is, a compound having a polyalkylene oxide skeleton and a glycidyloxyphenyl group is preferably used. As the polyalkylene oxide skeleton, a linear or branched alkylene group having 2 to 6 carbon atoms is preferably repeatedly bonded by an ether bond, More preferably, it is at least one selected from polyethylene oxide, polypropylene oxide, polybutylene oxide, and polytetramethylene oxide. When the number of carbons in the repeating unit is more than 6, crystallization is likely to occur, so that the effect of reducing the elastic modulus may not be expected.
As for the repeating number of a polyalkylene oxide, 2-50 are preferable. This is because an alkylene glycol residue having a number of repetitions of 1 cannot be expected to have a low elastic modulus effect, and if it exceeds 50, the viscosity of the liquid resin composition becomes too high and curability deteriorates. A more preferable repeating number is 2-10.

A diglycidyl ether compound in which a polyalkylene oxide group is introduced into a molecular chain needs to have a glycidyloxyphenyl group, which is low in reactivity with an glycidyloxy group bonded to an aliphatic group. This is because it is limited to Lewis acids and acid anhydrides. Such a compound can be obtained by a method as described in JP-A No. 2004-156024. That is, by obtaining a compound having ethylene oxide as a repeating unit and having a phenolic hydroxyl group at both ends by acetalization reaction of bisphenol A and triethylene glycol divinyl ether, and further reacting with epichlorohydrin, both ends are glycidyloxyphenyl groups. To obtain a compound having a polyalkylene oxide skeleton. Similarly, polyalkylene oxide skeleton can be changed by selecting polypropylene oxide divinyl ether, polybutylene oxide divinyl ether, polytetramethylene oxide divinyl ether as the divinyl ether to be used. Instead, compounds having two phenolic hydroxyl groups in one molecule such as bisphenol compounds such as bisphenol F and biphenol or derivatives thereof, catechol, resorcinol, hydroquinone or derivatives thereof, naphthalenediol, anthracenediol, and the like can also be used.

  Usually, a solvent, a monofunctional epoxy compound or the like is used for the purpose of reducing the viscosity of the epoxy resin. Solvents are low-viscosity compounds such as methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, cyclohexanol, and γ-butyrolactone, and monofunctional epoxy compounds include phenyl glycidyl ether and cresyl glycidyl. This is a compound having one glycidyl group in one molecule such as ether. The solvent must be volatilized during the curing reaction and cannot be used because it may cause voids in the cured product or remain in the cured product. This is because the voids in the cured product cause peeling during the reflow treatment, and the solvent remaining in the cured product causes deterioration of properties at the time of heating such as adhesiveness at high temperatures. On the other hand, when a monofunctional epoxy compound is used, problems such as voids do not occur because it is incorporated into the system during the curing reaction, but the cohesive strength of the cured product is reduced because the molecular weight of the cured product does not increase sufficiently, This is because it causes a decrease in adhesive strength at a high temperature of 260 ° C. in particular. The compounding amount of the compound (B1) is preferably 10% by weight or more and 90% by weight or less with respect to the thermosetting resin (B). This is because it is difficult to achieve both adhesiveness and low stress even if the amount is less than this. A more preferable blending amount is 15% by weight or more and 60% by weight or less.

  In the present invention, the compound (B2) having two (meth) acryloyl groups in one molecule is preferably used. This is because the compound (B2) has low viscosity and is excellent in compatibility with a compound having two functional groups of the same kind in another molecule, and a reaction catalyst (reaction initiator) such as an organic peroxide is used. It is because it reacts quickly by doing. The number of functional groups contained in one molecule is limited to 2, but this is because when the number of functional groups is 1, the cohesive force of the cured product decreases and good adhesiveness cannot be maintained. This is because the elastic modulus of the cured product becomes too high and may cause peeling from the substrate or the like as a support.

The compound (B2) is not particularly limited as long as it has two (meth) acryloyl groups in one molecule. Glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) ) Acrylate, zinc di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) ) Acrylate, polybutanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1, 10-decane All di (meth) acrylate, tetramethylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, cyclohexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, cyclohexanediethanoldi (meth) acrylate, Cyclohexanedialkyl alcohol di (meth) acrylate, dimethanoltricyclodecane di (meth) acrylate, N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, 1,2-di (meth) ) Acrylamide ethylene glycol and the like. Among them, preferable compound B2 is ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol. Cold di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, Examples include cyclohexanedimethanol di (meth) acrylate and dimethanoltricyclodecane di (meth) acrylate. The compounding quantity of a compound (B2) is 10 to 40 weight% with respect to a thermosetting resin (B). A more preferable blending amount is 15% by weight or more and 30% by weight or less. If it is less than this, there is no sufficient effect for reducing the viscosity of the liquid resin composition, and if it is more than this, it may cause a decrease in adhesiveness.

  In the present invention, a compound (B3) having two maleimide groups in one molecule is used, but this has a highly polar maleimide group, whereby a liquid resin composition excellent in adhesiveness can be obtained. The compound (B3) is not particularly limited as long as it has two maleimide groups in one molecule, but preferably does not contain an aromatic ring. A compound containing an aromatic ring and having two maleimide groups generally has high crystallinity and is difficult to be liquefied even when mixed with compound (B1) and compound (B2), and even if it can be liquefied, it has a high workability. This is because only a liquid resin composition having a poor viscosity can be obtained, and a cured product obtained by the interaction between aromatic rings becomes brittle with poor toughness. In addition, the number of functional groups contained in one molecule is limited to two. This is because when the number of functional groups contained in one molecule is one, the cohesive force of the cured product is reduced, and as a result This is because the adhesive strength is reduced, and in the case of 3 or more, the crosslink density of the cured product is increased, and as a result, the elastic modulus of the cured product is high and the stress absorption property is decreased.

  A preferred compound (B3) is obtained by reacting a maleic amino acid obtained by the reaction of an aliphatic amino acid (a compound having a primary amino group and a carboxy group in one molecule) with maleic anhydride and an aliphatic diol. The compound is more preferably obtained by the reaction of maleimide amino acid and polyalkylene oxide diol. Since the compound obtained by the reaction of maleimide amino acid and polyalkylene oxide diol is liquid at room temperature, a liquid resin composition excellent in workability with low viscosity can be obtained when used in combination with compound (B1) and compound (B2). This is because the elastic modulus of the cured product can be lowered. Here, the number of carbon atoms of the polyalkylene oxide diol is preferably 2 to 6, and a linear or branched alkylene group is preferably repeatedly bonded by an ether bond. More preferably, it is at least one selected from polyethylene oxide, polypropylene oxide, polybutylene oxide, and polytetramethylene oxide. When the number of carbons in the repeating unit is more than 6, crystallization is likely to occur, so that the effect of reducing the elastic modulus may not be expected. As for the repeating number of a polyalkylene oxide, 2-50 are preferable. This is because an alkylene glycol residue having a number of repetitions of 1 cannot be expected to have a low elastic modulus effect, and if it exceeds this, the viscosity of the liquid resin composition becomes too high and the curability deteriorates. A more preferable repeating number is 2-10. The compounding amount of the compound (B3) is preferably 10% by weight or more and 90% by weight or less with respect to the thermosetting resin (B). A more preferable blending amount is 40% by weight or more and 85% by weight or less. This is because it is difficult to achieve both adhesiveness and low stress even if the amount is less than this.

  In addition to compounds (B1), (B2), and (B3), it is also possible to use a compound having two functional groups other than glycidyl group, (meth) acryloyl group, and maleimide group. Examples thereof include di (meth) allyl ester compounds such as diallyl ester of cyclohexanedicarboxylic acid, compounds obtained by transesterifying di (meth) allyl ester compounds and diols, divinyl ether compounds, and the like.

The curing catalyst (C) used in the present invention is for accelerating the reaction of the thermosetting resin (B), and even if it is compounded in a large amount, even a compound that functions as a curing agent can be used as a curing agent. When the amount is small, it is handled as a curing catalyst. Specifically, it is a compound that is blended in a small amount of less than 5% by weight with respect to the thermosetting resin (B) and accelerates the reaction of the thermosetting resin (B), and includes a compound usually called an initiator.
The curing catalyst (C) preferably used is an adduct of 2-methylimidazole and 2,4-diamino-6-vinyltriazine, 2-phenyl-4-methyl-5-hydroxymethylimidazole, dicyandiamide, organic peroxide. Is mentioned. It is also possible to use phosphorus compounds, amine compounds other than the above, and the like.

  The organic peroxide (C1) has an exothermic start temperature of 40 ° C. or more and 100 ° C. or less in a rapid heating test (decomposition start temperature when 1 g of a sample is placed on an electric heating plate and heated at 4 ° C./min). It is preferable to include. If the heat generation start temperature is lower than this, the storage stability of the liquid resin composition at normal temperature is deteriorated, and if it is higher than this, a void may be generated when the semiconductor element is bonded to the organic substrate with the liquid resin composition. This is because the organic substrate easily absorbs moisture unlike the metal lead frame, so that moisture is volatilized from the organic substrate during the curing and voids are formed in the cured product. Voids in the cured product are often undesirable because they cause peeling and cracks during reflow treatment. By setting the heat generation starting temperature to be equal to or lower than the boiling point of water, the formation of voids can be suppressed because the viscosity of the liquid resin composition is increased by the reaction at a lower temperature than the volatilization of water becomes intense.

  Specific examples of preferred organic peroxide (C1) include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis. (T-butylperoxy) cyclohexane, t-butylhydroperoxide, diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, benzoyl peroxide, diisopropylperoxydicarbonate Bis (4-t-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-sec-butylperoxy Carbonate, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneo Decanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) Hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t- Butyl peroxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t Butyl peroxy-2-ethylhexyl monocarbonate, and the like. Of these, bis (4-t-butylcyclohexyl) peroxydicarbonate, dilauroyl peroxide, and benzoyl peroxide are preferably used. These may be used alone or in combination of two or more, and may be used in combination with an organic oxide having an exothermic starting temperature of 100 ° C. or higher and 140 ° C. or lower in the rapid heating test described below. 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 2,2-bis (4,4-di-t-butyl) Peroxycyclohexyl) propane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, P-menthane hydroperoxide, 1,1,3 3-tetramethylbutyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2 , 5-Dimethyl-2,5-bis (t-butylperoxy) hexyne-3, t-butylperoxymaleic acid, t-butyl -Oxylaurate, t-butylperoxyisopropyl monocarbonate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butyl Peroxy-m-toluoyl benzoate, t-butyl peroxybenzoate, t-butyl peroxyallyl monocarbonate, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and the like.

Here, since the liquid resin composition of the present invention is usually used under illumination such as a fluorescent lamp, if a photopolymerization initiator is contained, an increase in viscosity is observed due to a reaction during use, so that the photopolymerization is substantially performed. It is not preferable to contain an initiator. “Substantially” means that a small amount of the photopolymerization initiator may be present to such an extent that no increase in viscosity is observed, and it is preferably not contained.
The compounding quantity of a curing catalyst (C) is less than 5 weight% with respect to a thermosetting resin (B). If the amount is larger than this, the elastic modulus of the cured product becomes too high, which causes a decrease in adhesive strength at high temperatures.

  The additive (D) used in the present invention is a coupling agent, an antifoaming agent, a surfactant and the like, and substantially contains a solvent and a monofunctional reactive diluent used for the purpose of lowering the viscosity. Absent. “Substantially not contained” means that, for example, even if a solvent is contained in various additives, the amount thereof is 1% by weight or less based on the thermosetting resin (B) + curing catalyst (C) + additive (D). Yes, more preferably 0.5% by weight or less, and particularly preferably not included.

  The liquid resin composition of the present invention can be produced, for example, by premixing each component, kneading using three rolls, and degassing under vacuum.

  A known method can be used as a method of manufacturing a semiconductor device using the liquid resin composition of the present invention. For example, using a commercially available die bonder, the liquid resin composition is dispensed onto a predetermined portion of the organic substrate, and then the chip is mounted and heat-cured. Thereafter, wire bonding is performed, and a semiconductor device is manufactured by transfer molding using an epoxy resin.

[Example 1]
The filler (A) is a flaky silver powder (hereinafter referred to as silver powder) having an average particle diameter of 8 μm and a maximum particle diameter of 30 μm, and the compound (B1) having two glycidyl groups in one molecule is obtained by a reaction of bisphenol A and epichlorohydrin. The resulting diglycidyl bisphenol A (epoxy equivalent 180, liquid at room temperature and having two glycidyl groups in one molecule, hereinafter referred to as compound B11) as compound (B2) having two (meth) acryloyl groups in one molecule Has 1,6-hexanediol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., Light Ester 1, 6HX, 2 methacryl groups in one molecule, hereinafter referred to as Compound B21), and 2 maleimide groups in one molecule. As the compound (B3), polyether bismaleimide acetate (Dainippon Ink Industries, Ltd., Lumicu AMIA-200, a reaction product of maleimidated glycine and polytetramethylene glycol diol having two maleimide groups in one molecule, the following compound B3), and bis (4-t-butylcyclohexyl) as the curing catalyst (C) ) Peroxydicarbonate (manufactured by NOF Corporation, Parroyl TCP, heat generation starting temperature in rapid heating test: 82 ° C., hereinafter referred to as compound C11), dicyandiamide (hereinafter referred to as compound C21), 2-phenyl-4-methyl-5-hydroxy Silane coupling agent having a glycidyl group as additive (D) (Shin-Etsu Chemical Co., Ltd., KBM-403E, hereinafter referred to as compound D1) ) As shown in Table 1, kneaded using three rolls and defoamed Give a liquid resin composition, shown in Table 1 the results of evaluation by the following evaluation methods. In addition, a mixture ratio is a weight part.

[Examples 2 to 8]
Evaluation was performed after blending at the ratio shown in Table 1 and obtaining a liquid resin composition in the same manner as in Example 1. In Example 4, dilauroyl peroxide (manufactured by NOF Corporation, Parroyl L, heat generation start temperature in a rapid heating test: 59 ° C., hereinafter referred to as compound C12) is used as the curing catalyst (C). As the curing catalyst (C), compound C11 and dicumyl peroxide (manufactured by NOF Corporation, Park Mill D, exothermic starting temperature in rapid heating test: 126 ° C., hereinafter referred to as compound C13) are incorporated into one molecule in Example 6 ( As a compound (B2) having two (meth) acryloyl groups, dimethacrylate of ethylene glycol (manufactured by Kyoeisha Chemical Co., Ltd., light ester EG, having two (meth) acryloyl groups in one molecule, hereinafter compound B22), In Example 7, polyalkylene oxide divinyl ether as a compound (B1) having two glycidyl groups in one molecule and Diglycidyl etherified product of reaction product of Sphenol A (EXA-4850-1000, manufactured by Dainippon Ink & Chemicals, Inc., having two glycidyl groups in one molecule, hereinafter compound B12) is cured in Example 8. 2-Phenyl-4-methyl-5-hydroxymethylimidazole (Curazole 2P4MHZ: manufactured by Shikoku Chemicals Co., Ltd., hereinafter referred to as Compound B23) was used as the catalyst (C).

[Comparative Examples 1-6]
Evaluation was performed after blending at the ratio shown in Table 1 and obtaining a liquid resin composition in the same manner as in Example 1. In Comparative Example 2, compound C13 was used, and in Comparative Example 3, ortho-cresol novolak glycidyl ether (softening point 70 ° C., epoxy equivalent 210, one or more glycidyl groups in one molecule, hereinafter referred to as compound E11) and cresyl glycidyl ether. (Epoxy equivalent 185, one compound having one glycidyl group in the molecule, hereinafter referred to as compound E12), compound E11 and methyl carbitol (solvent, hereinafter referred to as compound E31) in Comparative Example 4, and lauroyl methacrylate (Kyoeisha) in Comparative Example 5. Chemical ester, light ester L, 1 (meth) acryloyl group in the molecule, compound E21 below, trimethylolpropane trimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester TMP) in Comparative Example 6. Compound 3 having three (meth) acryloyl groups in one molecule 2) was used.

-Adhesive strength: Using a liquid resin composition shown in Table 1, a 6 x 6 mm silicon chip is formed on a PBGA substrate (size 35 x 35 mm, thickness 0.56 mm, core material: BT (bismaleimide-triazine) resin, solder Resist: Mounted on PSR4000AUS308 (manufactured by Taiyo Ink Manufacturing Co., Ltd.) and cured in an oven at 175 ° C. for 30 minutes, after curing and after moisture absorption (85 ° C., 85%, 72 hours), 260 ° C. using an automatic adhesive force measuring device The die shear strength when heated at a temperature of 260 ° C. was passed when the die shear strength when heated at 30 ° C. was 30 N / chip or more, and the unit of adhesive strength was N / chip.
Elastic modulus: 4 × 20 × 0.1 mm film-like test pieces were prepared using the liquid resin composition shown in Table 1 (curing conditions 175 ° C. for 30 minutes), and the dynamic viscoelasticity measuring machine (DMA) was used. The measurement was performed in the pull mode. The measurement conditions are as follows.
Measurement temperature: room temperature to 300 ° C
Temperature increase rate: 5 ° C / min Frequency: 10Hz
Load: 100mN
The storage elastic modulus at 250 ° C. was regarded as the elastic modulus, and the case of 500 MPa or less was regarded as acceptable. The unit of elastic modulus is MPa.

Void: Using the liquid resin composition shown in Table 1, a 9 × 9 mm glass chip was mounted on the PBGA substrate and cured in an oven at 175 ° C. for 30 minutes. After curing, the voids were visually observed. A void having an area of 10% or less with respect to the chip size was regarded as acceptable. The unit of void is%.
-Reflow resistance: Using the liquid resin composition shown in Table 1, the PBGA substrate and the silicon chip were cured and bonded at 175 ° C for 30 minutes. The die-bonded PBGA substrate is encapsulated with a sealing material (Sumicon EME-G770, manufactured by Sumitomo Bakelite Co., Ltd.) to form a semiconductor device (package). Treatment (260 ° C., 10 seconds, 3 reflows) was performed. The degree of peeling of the treated package was measured with an ultrasonic flaw detector (transmission type). The case where the peeling area of the die attach part was less than 10% was regarded as acceptable. The unit of peeling area is%.
Package: 35 x 35mm PBGA
PBGA substrate: size 35 x 35 mm, thickness 0.56 mm
Core material: BT (bismaleimide-triazine) resin
Solder resist: PSR4000AUS308
(Manufactured by Taiyo Ink Manufacturing Co., Ltd.)
Chip size: 9x9mm
Liquid resin composition curing conditions: 175 ° C. for 30 minutes in oven

  The liquid resin composition of the present invention exhibits good adhesion and low elastic modulus, and since no voids are generated during curing, the use of the present invention as a die attach material has unprecedented high reliability. It can be suitably used for a semiconductor device.

Claims (5)

It consists of (A) a filler, (B) a thermosetting resin, (C) a curing catalyst, and (D) an additive, and the thermosetting resin (B) has two functional groups of the same type in one molecule. A compound consisting only of a compound (B1) having two glycidyl groups in one molecule, a compound (B2) having two (meth) acryloyl groups in one molecule, and two maleimide groups in one molecule A liquid resin composition comprising a compound (B3). The liquid resin composition according to claim 1, wherein the curing catalyst (C) contains an organic peroxide (C1). The liquid resin composition according to claim 2, wherein the organic peroxide (C1) contains a compound having an exothermic start temperature in a rapid heating test of 40 ° C. or more and 100 ° C. or less. The liquid resin composition according to claim 1, wherein the liquid resin composition is for bonding a semiconductor element and an organic substrate. A semiconductor device manufactured using the liquid resin composition according to claim 1 as a die attach material.