JP5571730B2 - Thermosetting resin composition and semiconductor device - Google Patents

Description

  The present invention relates to, for example, a conductive paste for mounting a semiconductor component, particularly a thermosetting resin composition used as a thermosetting low-temperature solder paste, and a semiconductor device in which the semiconductor component is mounted using the thermosetting resin composition It is about.

  In recent years, as the density of semiconductor devices such as semiconductor packages has increased and the number of pins has increased, there has been a rapid increase in methods to replace the method of mounting on circuit boards by soldering using leads, such as the conventional QFP (Quad Flat Package). ing. A typical example of such a method is a method of mounting on a circuit board using solder balls (solder bumps) such as BGA (Ball Grid Array) and CSP (Chip Size Package).

  Conventionally, when a semiconductor component is mounted on a circuit board or the like, a material called cream solder has been used.

  Cream solder is a composition containing solder particles, a flux component, and a solvent. In component mounting using the cream solder, the solder particles are melted by heating the cream solder to a temperature equal to or higher than the melting point of the solder particles in a reflow furnace. At the same time, the oxide layer on the surface of the solder particles is removed by the flux component at a high temperature, and the solder particles are integrated, thereby ensuring conduction between the conductor wiring such as a circuit board and the semiconductor component. In a component mounting process (solder reflow process) using such cream solder, many components can be connected together, and productivity can be improved.

  As the flux component to be added, rosin component materials represented by abietic acid, various amines and salts thereof, and high melting point organic acids such as sebacic acid and adipic acid are known.

  In recent years, so-called Pb-free solder has begun to be used instead of Pb eutectic solder, which is a typical representative solder. As the Pb-free solder, for example, Sn—Ag—Cu solder, solder using a low melting point metal such as Bi, and the like are known. Conventional Pb eutectic solder, which is a typical representative solder, has a melting point of 183 ° C., while Sn—Ag—Cu based solder, which is a typical Pb-free solder, has a higher melting point by about 30 ° C. . For this reason, in the conventional solder reflow process, component mounting is performed at a maximum temperature of 215 to 260 ° C.

  As suitable for such Pb-free solder, the present inventors proceeded with the development of a thermosetting resin composition in which a thermosetting resin such as an epoxy resin is blended as a resin component and the resin is thermoset together with melting of the solder. (For example, see Patent Documents 1 to 3). This thermosetting resin composition functions as cream solder.

JP 2009-263500 A JP 2010-077265 A JP 2012-025918 A

  However, since BGA and CSP are often used in mobile devices such as cellular phones, the mounting structure of BGA and CSP is required to have drop impact resistance.

  The present invention has been made in view of the circumstances as described above, and provides a thermosetting resin composition capable of improving the drop impact resistance and a semiconductor device on which a semiconductor component is mounted using the thermosetting resin composition. Is an issue.

（式中、Ｒ1およびＲ2はそれぞれ独立に水素原子またはメチル基を示し、Ｒ3はそれぞれ独立にメチル基、塩素原子、または臭素原子を示し、ａは０〜２の整数を示す。Ｘは、エチレンオキシエチル基、ジ（エチレンオキシ）エチル基、トリ（エチレンオキシ）エチル基、プロピレンオキシプロピル基、ジ（プロピレンオキシ）プロピル基、トリ（プロピレンオキシ）プロピル基、または炭素数２〜１５のアルキレン基を示す。ｍは自然数でありその平均は１．２〜５である。）で表される構造を有する直鎖状２官能エポキシ樹脂（Ａ）、および次の式（II）：

（式中、Ｒ4およびＲ5はそれぞれ独立に水素原子またはメチル基を示し、Ｒ6はそれぞれ独立に炭素数１〜１０の炭化水素基またはハロゲン原子を示し、ｂは０〜４の整数を示す。ｎは自然数でありその平均は２５〜５００である。）で表される構造を有する重量平均分子量（Ｍｗ）１５０００〜７００００の直鎖状２官能フェノキシ樹脂（Ｂ）から選ばれる少なくとも１種を含み、前記硬化剤は、酸無水物基の残基として全炭素数のうち７０％以上が主鎖のアルキレン基またはアルキル基を構成する炭素数７〜２０の炭化水素基を有する酸無水物当量２００〜４００の脂肪族酸無水物からなる酸無水物硬化剤を含むことを特徴とする。 In order to solve the above problems, the thermosetting resin composition of the present invention is a thermosetting resin composition containing solder particles having a melting point of 240 ° C. or less, a thermosetting resin binder, and a flux component. rESIN binder contains an epoxy resin and a curing agent, the epoxy resin, the following formula (I):

(Wherein R1 and R2 each independently represent a hydrogen atom or a methyl group, R3 each independently represents a methyl group, a chlorine atom or a bromine atom, and a represents an integer of 0 to 2. X represents ethylene. Oxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, or alkylene group having 2 to 15 carbon atoms M is a natural number and the average is 1.2 to 5.) A linear bifunctional epoxy resin (A) having a structure represented by the following formula (II):

(In the formula, R 4 and R 5 each independently represent a hydrogen atom or a methyl group, R 6 independently represents a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and b represents an integer of 0 to 4. n see contains at least one is a natural number average is selected from a 25 to 500.) the weight average molecular weight having a structure represented by (Mw) 15,000 to 70,000 linear bifunctional phenoxy resin (B) The curing agent has an acid anhydride equivalent of 200 % of the total number of carbon atoms as the residue of the acid anhydride group, and the hydrocarbon group having 7 to 20 carbon atoms constituting the main chain alkylene group or alkyl group. 400 of acid anhydride hardener ing from aliphatic acid anhydride, characterized in including it.

In the thermosetting resin composition, the epoxy resin, including it is preferable to both linear bifunctional epoxy resin (A) and linear bifunctional phenoxy resin (B).

In this thermosetting resin composition, a linear bifunctional epoxy resin represented by the formula (I) (
Preferably it contains 50 to 95 wt% of A) to the epoxy resin total amount.

In the thermosetting resin composition preferably contains 1 to 20 wt% of linear bifunctional phenoxy resin represented by the formula (II) (B) with respect to the epoxy resin total amount.

In the thermosetting resin composition preferably contains 50 to 95 wt% of the acid anhydride curing agent to the curing agent total amount.

  A semiconductor device of the present invention is characterized by including a joint portion in which a terminal of a semiconductor component and an electrode of a circuit board are joined using the thermosetting resin composition described above.

  According to the thermosetting resin composition of the present invention, the drop impact resistance of a semiconductor device on which a semiconductor component is mounted can be improved.

  According to the semiconductor device of the present invention, the drop impact resistance can be improved.

  The present invention is described in detail below.

  The thermosetting resin composition according to the present invention contains solder particles having a melting point of 240 ° C. or less, a thermosetting resin binder, and a flux component.

  As the solder particles, solder particles having a melting point of 240 ° C. or lower are used.

  Although the minimum of melting | fusing point of a solder particle is not specifically limited, It is preferable that it is 130 degreeC or more.

  Although it does not specifically limit as a solder particle, For example, the alloy etc. which were based on Sn can be used. Specifically, for example, an alloy of Sn and a metal such as Ag, Cu, Bi, Zn, or In can be used.

  The content of solder particles in the thermosetting resin composition is preferably in the range of 40 to 95% by mass, and more preferably in the range of 70 to 95% by mass. Within this range, the electrical bondability of the semiconductor component by the cured product of the thermosetting resin composition and the reinforcing effect by the thermosetting resin binder can be sufficiently exerted, and the coating workability is reduced by increasing the viscosity. Can also be suppressed.

  The thermosetting resin binder contains an epoxy resin and a curing agent as main components. Epoxy resin cures at a relatively low temperature and has high adhesiveness, so it can exhibit sufficient curability even at lower temperatures than conventional solder reflow treatment to enable component mounting and exhibit a sufficient reinforcing effect. .

  As the epoxy resin, at least one flexible epoxy resin selected from a linear bifunctional epoxy resin (A) and a linear bifunctional phenoxy resin (B) is used.

  Drop impact resistance can be improved by using these flexible epoxy resins in combination with a flexible curing agent described later.

  The linear bifunctional epoxy resin (A) includes an aromatic hydrocarbon group (a1) having a bonding site with another group in the aromatic nucleus, and a hydrocarbon group (a2) or other hydrocarbon group containing an ether bond. (A3) has a structure bonded via an acetal bond (a4). And it has the structure which the glycidyloxy group couple | bonded with the said aromatic hydrocarbon group (a1).

  Here, the aromatic hydrocarbon group (a1) having a binding site in the aromatic nucleus is a hydrocarbon group having a binding site with another structural unit in the aromatic nucleus in the aromatic hydrocarbon compound. Specific examples of such an aromatic hydrocarbon group (a1) include (i) a hydrocarbon group having a structure having only one benzene ring, and (ii) a benzene ring bonded through a single bond. (Iii) a hydrocarbon group having a structure in which a benzene ring is bonded via an aliphatic carbon atom, and (iv) a structure in which the benzene ring is bonded via an aliphatic cyclic hydrocarbon group. (V) a hydrocarbon group having a structure in which a plurality of benzene rings are condensed and polycyclic, (vi) a hydrocarbon group having a structure in which benzene rings are bonded via an aralkyl group, and the like.

  Among these structures, an aromatic hydrocarbon group represented by the structure (iii) is preferable, and a methylenediphenylene group and a 2,2-propane-diphenyl group are particularly preferable.

  The hydrocarbon group (a2) or other hydrocarbon group (a3) containing an ether bond functions as a flexible skeleton. That is, it functions as a soft segment that imparts flexibility to the linear bifunctional epoxy resin (A), and the cured product obtained by curing the linear bifunctional epoxy resin (A) becomes extremely flexible. . The hydrocarbon group (a2) containing an ether bond is preferably an alkyleneoxyalkylene group (a2-1), and the other hydrocarbon group (a3) is a linear alkylene group having 2 to 15 carbon atoms (a3). -1) is preferred.

  Here, the alkyleneoxyalkylene group (a2-1) is formed by, for example, polyaddition reaction of ethyleneoxyethyl group, poly (ethyleneoxy) ethyl group, and propylene oxide formed by polyaddition reaction of ethylene oxide. In addition to the propyleneoxypropyl group and poly (propyleneoxy) propyl group, an ethyleneoxy group and a propyleneoxy group obtained by copolyaddition reaction of ethylene oxide and propylene oxide may coexist.

  On the other hand, the linear alkylene group (a3-1) having 2 to 15 carbon atoms is substantially composed of a linear carbon atom chain. Although a branched structure may be partially adopted so as not to affect the flexibility, a linear alkylene group having no branch is preferable from the viewpoint of flexibility.

  As a specific chemical structure of such a linear bifunctional epoxy resin (A), a structure represented by the above formula (I) is preferable, and a linear bifunctional epoxy resin represented by the above formula (I) ( Examples of A) include those having the following structural formulas.

  In this thermosetting resin composition, the linear bifunctional epoxy resin (A) represented by the formula (I) is preferably contained in an amount of 50 to 95% by mass based on the total amount of the epoxy resin. Within this range, the drop impact resistance can be improved, and the deterioration of workability can be suppressed.

  The linear bifunctional phenoxy resin (B) is a polyhydroxy polyether having an epoxy group synthesized from an epoxy resin such as bisphenol A type or bisphenol F type. The weight average molecular weight (Mw) is 15000-70000, preferably 30000-70000.

  Here, the weight average molecular weight is a value using a standard polystyrene calibration curve by gel permeation chromatography (GPC). Further, those having a mass average molecular weight / number average molecular weight in the range of 2 to 3 are particularly preferred.

  Among these, a linear bifunctional phenoxy resin (B) represented by the above formula (II) is preferable. By using this, the drop impact resistance can be particularly improved.

  In this thermosetting resin composition, the linear bifunctional phenoxy resin (B) represented by the formula (II) is preferably contained in an amount of 1 to 20% by mass based on the total amount of the epoxy resin. Within this range, the drop impact resistance can be improved, and the deterioration of workability can be suppressed.

  Moreover, it is preferable that this thermosetting resin composition contains both a linear bifunctional epoxy resin (A) and a linear bifunctional phenoxy resin (B) as a flexible epoxy resin. By containing both of these, the drop impact resistance can be improved synergistically, and the drop impact resistance can be particularly remarkably improved.

  In addition to these flexible epoxy resins, the epoxy resin that is liquid at room temperature can be blended with the thermosetting resin binder. When a liquid epoxy resin is used at room temperature, other components such as solder particles can be easily dispersed. In the present specification, “liquid at normal temperature” means having fluidity in a temperature range of 5 to 28 ° C. under atmospheric pressure, particularly around 18 ° C. at room temperature.

  The epoxy resin that is liquid at room temperature is not particularly limited as long as it has two or more epoxy groups in one molecule, and various types can be used.

  Specifically, for example, various liquid epoxy resins such as glycidyl ether type, glycidyl amine type, glycidyl ester type, and olefin oxidation type (alicyclic) can be used.

  More specifically, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, hydrogenated bisphenol type epoxy resins such as hydrogenated bisphenol A type epoxy resins and hydrogenated bisphenol F type epoxy resins, Biphenyl type epoxy resin, naphthalene ring-containing epoxy resin, alicyclic epoxy resin, dicyclopentadiene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, aliphatic epoxy resin, tri Glycidyl isocyanurate or the like can be used. These may be used alone or in combination of two or more.

  Among these, bisphenol-type epoxy resins and hydrogenated bisphenol-type epoxy resins are preferred as liquid epoxy resins at room temperature in consideration of lowering the viscosity of the liquid epoxy resin composition for semiconductor encapsulation and improving the physical properties of the cured product.

  Moreover, a solid epoxy resin can also be used together at normal temperature. As an epoxy resin that is solid at room temperature, for example, a biphenyl type epoxy resin, a dicyclopentadiene type epoxy resin, a triazine skeleton epoxy resin, or the like can be used.

  In the thermosetting resin binder, a flexible acid anhydride curing agent composed of an aliphatic acid anhydride having an acid anhydride equivalent of 200 to 400 is blended as a curing agent.

  Drop impact resistance can be improved by using this flexible acid anhydride curing agent in combination with the above-described flexible epoxy resin.

  Among these flexible acid anhydride curing agents, those having a hydrocarbon group having 7 to 20 carbon atoms as the residue of the acid anhydride group are preferable. In particular, from the viewpoint of improving the drop impact resistance by the flexible skeleton, it is preferable that 70% or more of the total carbon number of the residue has a hydrocarbon group constituting an alkylene group or an alkyl group of the main chain.

  Specific examples of such aliphatic acid anhydrides include octenyl succinic anhydride and 3-dodecenyl succinic anhydride.

  In this thermosetting resin composition, it is preferable that the flexible acid anhydride curing agent is contained in an amount of 50 to 95% by mass with respect to the total amount of the curing agent. Within this range, the drop impact resistance can be improved, and the deterioration of workability can be suppressed.

  As the curing agent, together with this flexible acid anhydride curing agent, acid anhydrides, phenol novolacs, various thiol compounds, various amines, dicyandiamide, imidazoles, metal complexes and their adduct compounds, for example, polyamine adducts Modified products can be used in combination. Among these, in view of improving workability, a liquid curing agent such as methylhexahydrophthalic anhydride is preferable.

  Although the usage-amount of a hardening | curing agent is set suitably, it is preferable to make it make the stoichiometric equivalent ratio of the hardening | curing agent with respect to the epoxy equivalent of an epoxy resin become the range of 0.8-1.2.

  In addition to the epoxy resin and the curing agent, the thermosetting resin binder can further contain other components as necessary. For example, a curing accelerator can be blended.

  As the curing accelerator, various imidazoles can be used. Examples of imidazoles include 2MZ, C11Z, 2PZ, 2E4MZ, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, 2E4MZ-CN, 2PZ-CN, C11Z-CN, 2PZ-CNS, C11Z-CNS, 2MZ-A, and C11Z. -A, 2E4MZ-A, 2P4MHZ, 2PHZ, 2MA-OK, 2PZ-OK (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name) and compounds obtained by adding these imidazoles to an epoxy resin can be mentioned. In addition, it is also possible to use a microcapsule obtained by coating these curing agents with a polyurethane-based or polyester-based polymer substance.

  As the curing accelerator, in addition to the imidazoles, for example, tertiary amines, 1,8-diazabicyclo (5.4.0) undecene-7, 1,5-diazabicyclo (4.3.0) nonene-5, etc. Cyclic amines and their tetraphenylborate salts, trialkylphosphines such as tributylphosphine, triarylphosphines such as triphenylphosphine, tetraphenylphosphonium tetraphenylborate and tetra (n-butyl) phosphonium tetraphenylborate Metal complexes such as quaternary phosphonium salts and Fe acetylacetonate and their adduct compounds can be used.

  The blending amount of these curing accelerators is appropriately set in consideration of gelation time and storage stability.

  The flux component blended in the thermosetting resin composition of the present invention is not particularly limited, and rosin component materials represented by abietic acid, various amines and salts thereof, sebacin salt, adipic acid, glutaric acid An organic acid such as can be used.

  These flux components may be one type of component, or two or more types of components may be mixed.

  Among these flux components, abietic acid, adipic acid, and glutaric acid are more preferable because of high flux activity and high stability as a compound.

  It is preferable that content of a flux component is 1-50 mass% with respect to the total amount of a flux component and a thermosetting resin binder. In this case, the flux component exhibits an excellent flux action, and the mechanical bondability and electrical bondability of the cured product of the thermosetting resin composition can be further improved.

  Although the content of the flux component in the thermosetting resin composition is appropriately set, the content of the flux component is particularly preferably in the range of 1 to 50 phr with respect to the content of the thermosetting resin binder. Thus, the flux component exhibits a sufficient effect as a flux by setting the content to 1 phr or more. Further, when the content is 50 phr or less, the cured product of the thermosetting resin composition can exhibit a sufficient reinforcing effect during component mounting.

  The total amount of the thermosetting resin binder and the flux component in the thermosetting resin composition is preferably in the range of 5 to 30% by mass with respect to the total amount of the composition. By making the content 5% by mass or more, it is possible to impart good fluidity to the thermosetting resin composition and to suppress the generation of voids when the solder particles are integrated, which is further excellent A reinforcing action can be exhibited. Further, by setting the content to 30% by mass or less, a sufficient amount of solder particles can be secured in the thermosetting resin composition, and the solder particles can be easily fused and integrated. The connection resistance can be made sufficiently low.

  In addition to the above essential components, the thermosetting resin composition of the present invention may contain commonly used modifiers, additives, and the like. Moreover, a low boiling-point solvent and a plasticizer can also be added in order to reduce the viscosity of a thermosetting resin composition and to provide fluidity. Furthermore, it is also effective to add hardened castor oil or stearamide as a thixotropic agent for maintaining the printed shape.

  A thermosetting resin composition can be prepared by the following method, for example. First, solder particles having a melting point of 240 ° C. or less, a part or all of the epoxy resin, and a flux component are mixed. When a part of the epoxy resin is used in the mixture, the remainder and a curing agent are added and mixed.

  At this time, when the components contained in the thermosetting resin binder such as an epoxy resin and a curing agent are in a liquid state, the components can be easily mixed.

  And if manufactured in this way, the thermosetting resin composition can be obtained by mixing the flux components around the solder particles, and the storage stability at room temperature and the flux action during heating are efficiently expressed. can do.

  Since the thermosetting resin composition thus obtained contains an epoxy resin and a curing agent as a thermosetting resin binder as described above, an increase in viscosity at room temperature is suppressed. For this reason, the storage stability is high.

  By using the thermosetting resin composition of the present invention, a semiconductor component can be mounted on a circuit board or the like having conductor wiring. A semiconductor device of the present invention includes a joint portion in which a terminal of a semiconductor component and an electrode of a circuit board are joined using the thermosetting resin composition.

  For example, when a chip component for surface mounting is used as a semiconductor component and a printed wiring board is used as a circuit board, a thermosetting resin composition is applied to electrodes (pads) on the printed wiring board. Here, as a circuit board, for example, a rigid printed wiring board formed by providing a conductive pattern on a glass epoxy laminated board, a polyimide film, a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, etc. A flexible printed wiring board formed with a pattern can be used.

  The thermosetting resin composition can be applied, for example, by superimposing a metal mask having a through hole at the same position as the electrode on the circuit board, and then applying the thermosetting resin composition supplied to the surface of the metal mask with a squeegee. This can be done by filling the through hole.

  Thereafter, when the metal mask is separated from the circuit board, a circuit board coated with the thermosetting resin composition for each electrode can be obtained.

  Next, the semiconductor component and the circuit board are stacked using a chip mounter or the like so that the terminal of the semiconductor component and the electrode of the circuit board face each other while the thermosetting resin composition is in an uncured state. Here, as semiconductor parts, in addition to semiconductor packages such as CSP and BGA formed by providing solder balls as terminals and QFP formed by providing leads as terminals, terminals are provided without being accommodated in the package. A semiconductor element (bare chip) can be used.

  In this state, the thermosetting resin composition is heated to a predetermined heating temperature by, for example, a solder reflow process in which the printed wiring board on which the chip components are arranged is heated in a reflow furnace.

  This heating temperature is set to an appropriate temperature at which the solder particles are sufficiently melted and the curing reaction of the thermosetting resin binder proceeds sufficiently.

  The heating temperature is preferably set so that the curing reaction of the epoxy resin proceeds before the solder particles are completely melted and the aggregation of the solder particles is not hindered.

  The preferable heating temperature for that is not less than a temperature 10 ° C. higher than the melting point of the solder particles and not more than 60 ° C. higher than the melting point of the solder particles.

  Then, it heats to the temperature which the solder particle in the thermosetting resin composition and the solder ball which forms the terminal of a semiconductor component fuse | melt by a reflow system. By curing the thermosetting resin composition by this heating, a bonding portion that electrically connects the semiconductor component and the circuit board is provided. That is, the heated solder particles and the solder balls are integrated to form a solder portion, and the thermosetting resin binder in the thermosetting resin composition is cured so as to cover the periphery of the solder portion. Thus, the resin cured portion is formed. As described above, the joint portion is formed by a solder portion in which the solder particles and the solder balls are fused and integrated, and a resin cured portion that covers the periphery of the solder portion.

  When the thermosetting resin composition is heated, the solder particles are melted and the flux component in the thermosetting resin composition exhibits a flux action.

  This flux action removes the oxide layer on the surface of the solder particles, promotes the integration of the solder particles, and melts and joins the solder particles to the electrodes and terminals, and between the terminals of the chip component and the electrodes of the printed wiring board. An electrical connection is made.

  Further, the thermosetting reaction of the epoxy resin and the curing agent contained as the thermosetting resin binder proceeds, and the semiconductor component and the circuit board are mechanically joined. Thereby, the semiconductor component is mounted on the circuit board, and the semiconductor device is manufactured.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In addition, the compounding quantity shown in Table 1 and Table 2 represents a mass part.

As the blending components shown in Table 1 and Table 2, the following were used.
(Solder particles)
The solder composition defined in JIS H42B: 58A was used (Sn42Bi58). Solder particles were produced according to a conventional method. The solder particles had an average particle size of 15 μm and a melting point of 139 ° C.
(Thermosetting resin binder)
1. Epoxy resin
(1) Liquid epoxy resin, “Epototo YD128” manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent of 184 to 194, bisphenol A type epoxy resin
(2) Flexible epoxy resin 1, "EXA-4850" manufactured by DIC Corporation, epoxy resin having a structure represented by the above formula (I)
(3) Flexible epoxy resin 2, “jER4250” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 7500-8900, solid at normal temperature, bis A / bis F mixed type, Mw about 60000, structure represented by the above formula (II) 1. Epoxy resin having Hardener
(1) "Epiclon B-650" manufactured by DIC Corporation, methylhexahydrophthalic anhydride
(2) "Ricacid OSA" manufactured by Shin Nippon Rika Co., Ltd., octenyl succinic anhydride, acid anhydride equivalent 258 g / eq
3. Curing Accelerator “Cureazole 2MA-OK” manufactured by Shikoku Kasei Kogyo Co., Ltd., 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct
(Flux component)
Abietic acid

  Solder particles, a flux component, and an epoxy resin were uniformly kneaded using a disper, and the kneaded product was left for a whole day and night. On the other hand, a thermosetting resin composition was prepared by mixing a curing agent and an epoxy resin to prepare a composition, adding the composition to the kneaded material, and mixing the mixture uniformly.

  Next, this thermosetting resin composition was supplied to an Au plated electrode on a circuit board (FR-4 board) so as to have a thickness of 0.1 mm by screen printing.

  Thereafter, a CSP package having a size of 14 mm □, a thickness of 0.8 mm, a ball diameter of 0.25 mm, and a pitch of 0.4 mm was accurately mounted on a circuit board using a flip chip bonder. Then, it connected by heating (160 degreeC 6 minutes) with a reflow apparatus.

  A drop test of the CSP package was performed on the evaluation CSP package thus obtained. The circuit board was set on a drop impact test jig compliant with the JEITA standard, and dropped 10 times continuously at a drop height of 1 m.

  Thereafter, the connectivity of the CSP package was determined based on the presence or absence of conduction of the daisy chain pattern composed of the ball connection portions (a total of 552).

  In this daisy chain pattern, the places where the presence / absence of conduction can be checked is divided into eight places, and the presence / absence of conduction can be checked every eight places. It was evaluated how many of these eight locations were OK.

  The results are shown in Tables 1 and 2.

  From Table 1, in Examples 1-9, at least 1 type of flexible epoxy resin chosen from linear bifunctional epoxy resin (A) and linear bifunctional phenoxy resin (B) was used as an epoxy resin. . At the same time, a flexible acid anhydride curing agent comprising an aliphatic acid anhydride having an acid anhydride equivalent of 200 to 400 was used as the curing agent. As a result, in Examples 1 to 9, the drop impact resistance could be improved.

  In Examples 1 to 9, the chain bifunctional epoxy resin (A) is 50 to 95% by mass with respect to the total amount of the epoxy resin, and the linear bifunctional phenoxy resin (B) is 1 with respect to the total amount of the epoxy resin. It was used in the range of ˜20% by mass. Moreover, the soft acid anhydride hardening | curing agent was used in 50-95 mass% with respect to the hardening | curing agent whole quantity. And a liquid epoxy resin and a liquid hardening | curing agent were used together. As a result, it was possible to suppress deterioration of workability.

  In particular, in Examples 3, 8, and 9 in which both the linear bifunctional epoxy resin (A) and the linear bifunctional phenoxy resin (B) were blended as the flexible epoxy resin, there were places where conduction failure occurred. There was no one. That is, even compared with Examples 1, 2, 4 to 7, the drop impact resistance could be particularly remarkably improved.

  On the other hand, from Table 2, in the case of Comparative Examples 1 to 4 in which the flexible epoxy resin and the flexible acid anhydride curing agent are not used in combination, even if any one of them is used, conduction cannot be ensured after dropping. The drop impact resistance decreased.

Claims (6)

Mp 240 ° C. or less of the solder particles, a thermosetting resin binder, and the thermosetting resin composition containing a flux component, the thermosetting resin binder contains an epoxy resin and a curing agent, the epoxy resin, the following Formula (I):

(Wherein R1 and R2 each independently represent a hydrogen atom or a methyl group, R3 each independently represents a methyl group, a chlorine atom or a bromine atom, and a represents an integer of 0 to 2. X represents ethylene. Oxyethyl group, di (ethyleneoxy) ethyl group, tri (ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, or alkylene group having 2 to 15 carbon atoms M is a natural number and the average is 1.2 to 5.) A linear bifunctional epoxy resin (A) having a structure represented by the following formula (II):

(In the formula, R 4 and R 5 each independently represent a hydrogen atom or a methyl group, R 6 independently represents a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and b represents an integer of 0 to 4. n see contains at least one is a natural number average is selected from a 25 to 500.) the weight average molecular weight having a structure represented by (Mw) 15,000 to 70,000 linear bifunctional phenoxy resin (B) The curing agent has an acid anhydride equivalent of 200 % of the total number of carbon atoms as the residue of the acid anhydride group, and the hydrocarbon group having 7 to 20 carbon atoms constituting the main chain alkylene group or alkyl group. the thermosetting resin composition, wherein the including that the name Ru acid anhydride curing agent from 400 aliphatic acid anhydride. Before disappeared epoxy resin, said linear bifunctional epoxy resin (A) and the thermosetting resin according to claim 1, characterized in including that both the linear bifunctional phenoxy resin (B) Composition. The thermosetting resin according to claim 1 or 2 , wherein the linear bifunctional epoxy resin (A) represented by the formula (I) is contained in an amount of 50 to 95% by mass based on the total amount of the epoxy resin. Composition. According to any one of claims 1 to 3, characterized in that it contains 1 to 20 mass% said formula (II) linear bifunctional phenoxy resin represented by (B) to the epoxy resin total amount Thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 4, the pre-hexane anhydride curing agent, characterized in that it contains 50 to 95 wt% with respect to the curing agent total amount. A semiconductor device comprising: a junction part in which a terminal of a semiconductor component and an electrode of a circuit board are joined using the thermosetting resin composition according to any one of claims 1 to 5 .