JP2013256584A - Thermosetting resin composition, flux composition, and semiconductor apparatus using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition capable of performing component packaging that is excellent in solder aggregation in a batch reflow step and is excellent in reliability to dropping impact and moisture absorption, and to provide a flux composition and a semiconductor apparatus using them.SOLUTION: A thermosetting resin composition comprises solder particles, a thermosetting resin binder, and a flux component. The thermosetting resin composition further comprises, as the flux component, a salt of a dicarboxylic or tricarboxylic acid and diethanol or triethanol amines.

Description

  The present invention relates to a thermosetting resin composition and a flux composition used for mounting a semiconductor component on a circuit board, for example, and a semiconductor device in which a semiconductor component is mounted using these.

  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, various mobile devices typified by mobile phones and smartphones have been put into practical use. However, due to the nature of being carried around, there is no problem with parts connection parts due to the impact when the device falls. In addition, improvement of component connection strength is desired.

  So-called underfill, in which strength is strengthened by applying an adhesive to the component connecting portion, is also effective, but improvement in the point that the assembly process is increased and the throughput is increased is desired.

  Then, the method of reinforcing an electrical connection part with a thermosetting resin simultaneously with reflow soldering is proposed, and practical use is advanced. Specifically, a composition containing a specific carboxylic acid as a flux component together with a thermosetting resin binder and solder particles has been proposed (Patent Document 1).

Japanese Patent No. 4535050

  However, in order for carboxylic acid to act as a flux in a thermosetting binder, it is usually necessary to add 10 to 50 PHR to the binder resin.

  If the blending amount is less than this, the solder particles are apparently integrated, but the solder particles called the ball residue remain in the resin, which is a factor of lowering electrical insulation and reliability.

  If a large amount of effective carboxylic acid is added, such a problem does not occur, but a large amount of carboxylic acid remains unreacted in the resin cured through the reflow process and remains as a plasticizer. For this reason, the cured resin becomes brittle, and sufficient reinforcement performance against drop impact cannot be obtained.

  Furthermore, the cured resin may easily absorb moisture, causing deterioration of insulation resistance due to moisture absorption, or adhesion reinforcement by resin may be hardly obtained due to moisture absorption.

  The present invention has been made in view of the circumstances as described above, and is a thermosetting resin composition that is excellent in solder cohesiveness in a batch reflow process and can be mounted with excellent reliability in terms of drop impact and moisture absorption. An object is to provide an object and a semiconductor device using the object.

  In addition, the present invention provides a flux that can act as a flux in mounting a semiconductor component by conductive connection of solder balls or solder bumps to obtain a good mounting property, and can act as a reinforcing resin to greatly increase its mounting strength. It is an object to provide a composition and a semiconductor device using the composition.

  In order to solve the above-described problems, the thermosetting resin composition of the present invention includes a dicarboxylic acid or a dicarboxylic acid as a flux component in a thermosetting resin composition containing solder particles, a thermosetting resin binder, and a flux component. It is characterized by containing a salt of tricarboxylic acid and diethanolamines or triethanolamines.

  In this thermosetting resin composition, the dicarboxylic acid or tricarboxylic acid is at least one selected from adipic acid, glutaric acid, diglycolic acid, propanetricarboxylic acid, citric acid, tartaric acid, oxalic acid, and succinic acid. Is preferred.

  The thermosetting resin composition of the present invention is a thermosetting resin composition containing solder particles, a thermosetting resin binder, and a flux component. As the flux component, a carboxylic acid anhydride and diethanolamines or triethanolamines are used. And an addition reaction product.

  In this thermosetting resin composition, the carboxylic acid anhydride is preferably at least one selected from glutaric acid anhydride, diglycolic acid anhydride, and succinic acid anhydride.

  In the thermosetting resin composition, the content of the flux component is preferably 1 to 10 PHR with respect to the thermosetting resin binder.

  In this thermosetting resin composition, the thermosetting resin binder is preferably an epoxy resin composition.

  The semiconductor device of the present invention is characterized in that it 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.

  The flux composition of the present invention is a thermosetting flux composition used as a flux for the conductive connection of solder balls or solder bumps, and contains a thermosetting resin binder and a flux component. Alternatively, it is characterized by containing a salt of tricarboxylic acid and diethanolamines or triethanolamines.

  The flux composition of the present invention is a thermosetting flux composition used as a flux for the conductive connection of solder balls or solder bumps, and contains a thermosetting resin binder and a flux component. It is characterized by containing an addition reaction product of an anhydride with diethanolamines or triethanolamines.

  A semiconductor device according to the present invention includes a joint portion in which a terminal of a semiconductor component and an electrode of a circuit board are joined by a solder ball or a solder bump, using the flux composition as a flux for a solder ball or a solder bump. It is a feature.

  According to the thermosetting resin composition of the present invention and a semiconductor device using the same, it is possible to mount components with excellent solder cohesiveness in a batch reflow process and excellent reliability against drop impact and moisture absorption.

  According to the flux composition of the present invention and the semiconductor device using the same, it acts as a flux in the mounting of semiconductor parts by conductive connection of solder balls or solder bumps, and good mountability is obtained, and also acts as a reinforcing resin. The mounting strength can be greatly increased.

  The present invention is described in detail below.

  The thermosetting resin composition of the present invention contains solder particles, a thermosetting resin binder, and a flux component.

  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 Pb, Ag, Cu, Bi, Zn, or In can be used.

  As the solder particles, those having an average particle diameter of 5 to 40 μm are usually used from the balance of cohesiveness and fillability.

  Although it does not specifically limit as a thermosetting resin binder, For example, an epoxy resin, a polyimide resin, a cyanate ester resin, a benzoxazine resin, a polyester resin etc. can be used in combination with a hardening | curing agent etc. suitably.

  In general, reflow mounting is performed at a temperature that is 10 to 20 ° C. higher than the melting point of the solder particles. However, in order to mount the component and to provide reinforcement, it has sufficient curability at that temperature. There is a need. In consideration of such points, an epoxy resin is particularly preferable because it is excellent in curability and adhesion in a short time at the reflow temperature.

  By using the epoxy resin composition as the thermosetting resin binder, the periphery of the melt-bonded solder can be covered with the cured epoxy resin, so that the bonding strength can be increased and the deterioration of the solder can be suppressed.

  And when using an epoxy resin composition as a thermosetting resin binder, a hardening agent is further mix | blended with an epoxy resin (usually liquid epoxy resin) and the hardening auxiliary component of a hardening | curing agent as needed.

  Here, as the liquid epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, alicyclic epoxy resin, novolac type epoxy resin, A naphthalene type epoxy resin or the like can be used.

  Moreover, what was liquefied by using a solid epoxy resin together can also be used. As the solid epoxy resin, for example, a biphenyl type epoxy resin, a dicyclopentadiene type epoxy resin, a triazine skeleton epoxy resin, or the like can be used.

  Although it does not specifically limit as a hardening | curing agent, For example, amines, imidazoles, phenols, acid anhydrides, hydrazides, polymercaptans, a Lewis acid-amine complex, etc. can be used.

  As the amine, a compound having at least one primary or secondary amino group in the molecule can be used, and is not particularly limited. For example, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylsulfide, metaxylene Diamine, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4 ′ -Diaminodiphenyl sulfide, 2,2-bis- [4- (4-aminophenoxy) phenyl] -hexafluoropropane, 2,2-bis (4-aminophenyl) -hexafluoropropane, 2,4-diaminotoluene, 1,4-diaminobenzene, 1,3-diaminobenzene, diethyltoluene Diamine, dimethyltoluenediamine, anilines, alkylated anilines, N-alkylated anilines and the like 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 the like, and compounds obtained by adding these imidazoles to an epoxy resin can be used. 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.

  Examples of phenols include bisphenol resin, phenol novolak resin, naphthol novolak resin, allylated phenol novolak resin, biphenol resin, cresol novolak resin, phenol aralkyl resin, cresol naphthol formaldehyde polycondensate, triphenylmethane type polyfunctional phenol resin. Xylylene-modified phenol novolak resin, xylylene-modified naphthol novolak resin, various polyfunctional phenol resins, and the like can be used.

  Examples of acid anhydrides include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylheimic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic acid Anhydride, 3,4-dimethyl-6- (2-methyl-1-propenyl) -1,2,3,6-tetrahydrophthalic anhydride, 1-isopropyl-4-methyl-bicyclo [2.2.2 Oct-5-ene-2,3-dicarboxylic anhydride and the like can be used.

  Although the usage-amount of a hardening | curing agent is not specifically limited, 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.

  Moreover, as a hardening accelerator, various imidazoles, various amines, various phosphorus compounds, metal complexes, such as Fe acetylacetonate, those adduct compounds, etc. can be used, for example.

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

  As the flux component, (1) a salt of dicarboxylic acid or tricarboxylic acid and diethanolamine or triethanolamine, or (2) an addition reaction product of carboxylic acid anhydride and diethanolamine or triethanolamine is used.

  The salt of (1) dicarboxylic acid or tricarboxylic acid and diethanolamines or triethanolamines is formed by an acid-base reaction. When dicarboxylic acid or tricarboxylic acid is mixed with liquid diethanolamines or triethanolamines, heat is generated even at room temperature, and a salt complex is formed by an acid-base reaction.

  It is preferable to complete the reaction between the liquids by heating to above the melting point of the dicarboxylic acid or tricarboxylic acid, but in many cases, even if it is less than the melting point, it becomes a completely uniform liquid property during heating, so it is necessary to heat to the melting point Absent.

  The mixing ratio of dicarboxylic acid or tricarboxylic acid to diethanolamines or triethanolamines is preferably 1: 0.5 to 1: 1 in terms of the molar ratio of carboxyl group to amino group. By setting the amino group to a molar ratio of 1: 0.5 or more, remaining molecules can be reduced without forming a salt, which is suitable for obtaining the effects of the present invention. By reducing the amino group to a molar ratio of 1: 1 or less, the amine compound is not salt-formed and the remaining molecules are reduced, and the pot life is increased when the hygroscopicity of the cured product is increased or a curing agent is added. It can suppress becoming worse.

  Although it does not specifically limit as dicarboxylic acid or tricarboxylic acid, For example, glutaric acid, succinic acid, malonic acid, oxalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, diglycolic acid, thiodiglycolic acid, phthalic acid Isophthalic acid, terephthalic acid, propanetricarboxylic acid, citric acid, tartaric acid and the like can be used.

  Among these, adipic acid, glutaric acid, diglycolic acid, propanetricarboxylic acid, citric acid, tartaric acid, oxalic acid, and succinic acid are preferable because they can exhibit flux activity in a smaller amount.

  The diethanolamines or triethanolamines are not particularly limited, and for example, triethanolamine, diethanolamine, methyldiethanolamine, ethyldiethanolamine and the like can be used.

  The addition reaction product of the carboxylic anhydride and the diethanolamines or triethanolamines of (2) is formed by these addition reactions.

  When carboxylic acid anhydride is mixed with liquid diethanolamines or triethanolamines, heat is generated even at room temperature, and an alcoholic hydroxyl group is added to the carboxylic acid anhydride to cause ring opening to form a half ester. It is done.

  It is preferable to complete the reaction between the liquids by heating above the melting point of the carboxylic acid anhydride, but in many cases it is not necessary to heat to the melting point because the liquid properties are completely uniform during heating even below the melting point. .

  The mixing ratio of carboxylic acid anhydride and amine is preferably 3: 1 to 1: 1 as the molar ratio of carboxylic acid anhydride to amino group. By setting the amino group to a molar ratio of 3: 1 or more, remaining molecules can be reduced without forming an adduct, which is suitable for obtaining the effects of the present invention. By reducing the amino group to a molar ratio of 1: 1 or less, adducts are not formed and the remaining molecules are reduced. When the hygroscopicity of the cured product is increased or a curing agent is added, the pot life is poor. It can suppress becoming.

  The carboxylic acid anhydride is not particularly limited. For example, glutaric anhydride, succinic anhydride, maleic anhydride, diglycolic anhydride, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, For example, methyltetrahydrophthalic anhydride can be used.

  Among these, glutaric acid anhydride, diglycolic acid anhydride, and succinic acid anhydride are preferable from the viewpoint that the flux activity can be exhibited with a smaller amount.

  The diethanolamines or triethanolamines are not particularly limited, and for example, triethanolamine, diethanolamine, methyldiethanolamine, ethyldiethanolamine and the like can be used.

  In the thermosetting resin composition of the present invention, the aforementioned salt (1) and addition reaction product (2) may be used singly or in combination of two or more. Moreover, you may use together with other generally used flux components.

  The content of the flux component is preferably in the range of 1 to 10 PHR and more preferably in the range of 3 to 10 PHR with respect to the thermosetting resin binder. When the content of the flux component is within this range, a sufficient effect as a flux can be exhibited, and the performance after curing of the thermosetting resin composition can be sufficiently obtained.

  The total amount of the thermosetting resin binder and the flux component is preferably in the range of 5 to 30% by mass with respect to the total amount of the thermosetting resin composition. When the total amount is 5% by mass or more, a flowable thermosetting resin composition can be obtained, and it is possible to suppress a lot of voids or a decrease in reinforcing action after the solder is integrated. When this total amount is 30% by mass or less, melting and integration of solder is promoted, and an increase in connection resistance can be suppressed.

  The thermosetting resin composition of the present invention may be blended with commonly used modifiers, additives and the like in addition to the components described above. 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, hydrogenated castor oil or stearamide can be added as a thixotropic agent for maintaining the printed shape.

  The thermosetting resin composition of the present invention can be produced by uniformly mixing or kneading solder particles, a thermosetting resin binder, a flux component, and other components as necessary using a disper or the like. it can.

  Since the flux component used in the thermosetting resin composition of the present invention has high activity, attention may be required for temperature and kneading share. This is because, when kneaded under severe conditions, an oxide film on the surface of the solder particles may be removed during production, and the particles may aggregate. Further, a production method in which the solvent is mixed in advance and the solvent is dried and removed later is also possible.

  Since the thermosetting resin composition of the present invention can achieve solder aggregation with a small amount of flux component, it can simultaneously achieve solder mounting and reinforcing resin formation without deteriorating the performance of the cured resin.

  The thermosetting resin composition of the present invention, like a normal solder paste (cream solder), is electrically bonded onto a semiconductor component bonding portion of a circuit board after a predetermined amount is supplied by a printing method or the like. Mount the electrodes of the semiconductor parts to be melted and melt the solder particles in a reflow furnace. Thereby, a semiconductor device in which the semiconductor component is electrically connected to the circuit board can be obtained.

  That is, a semiconductor component can be mounted on a circuit board or the like having conductor wiring using the thermosetting resin composition of the present invention. The 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 described above.

  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 thermosetting resin binder, for example, in the case of the epoxy resin composition, the thermosetting reaction of the epoxy resin and the curing agent 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.

  In addition to the aspects described above, in another aspect of the present invention, a flux composition is provided.

  In the embodiment described above, a solder particle is included to realize a process similar to that of cream solder. However, a semiconductor element such as a BGA, CSP, or flip chip in which solder is previously mounted on the package side is realized. For mounting, it is not always necessary to use a material containing solder particles.

  That is, if there is a material in which solder balls and solder bumps achieve fusion connection, solder connection can be achieved, and if the same thermosetting resin binder and flux component as the above-mentioned thermosetting resin composition are used, At the same time, a reinforced structure with a cured resin can be formed. Therefore, compared with the mounting using a normal flux, high joint strength can be achieved, and the thermal shock reliability and the drop impact property can be improved.

  That is, the flux composition of the present invention contains a thermosetting resin binder and a flux component. As the flux component, (1) a salt of dicarboxylic acid or tricarboxylic acid and diethanolamine or triethanolamine, or (2) an addition reaction product of cyclic carboxylic acid anhydride and diethanolamine or triethanolamine is used. .

  The specific composition of the flux composition of the present invention is the same as that of the above-mentioned thermosetting resin composition except for the solder particles. Moreover, you may mix | blend a small amount of solder particles in order to assist a joining process or to improve printability.

  By using this flux composition as a solder ball or solder bump flux, a semiconductor device in which a terminal of a semiconductor component and an electrode of a circuit board are bonded can be manufactured by the method described above, for example.

  The flux composition of the present invention can provide mounting performance equivalent to that of conventional flux in mounting a solder ball mounting package such as CSP, and acts as a reinforcing resin, and can greatly increase the mounting strength.

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.
Example 1
13.4 g (0.09 mol) of triethanolamine was added to 6.3 g (0.03 mol) of citric acid monohydrate, and citric acid was melted with stirring in a 120 ° C. oil bath for 5 minutes. This formulation is 1: 1 in terms of the molar ratio of carboxyl groups to amino groups. The obtained citric acid triethanolamine salt was a viscous liquid.

  As the solder particles, those manufactured by Mitsui Mining & Smelting Co., Ltd. (composition: Sn42 / Bi58, average particle size 15 μm, melting point 139 ° C.) were used. 81 parts by mass of this solder particle, 16.2 parts by mass of liquid epoxy resin YD128 (manufactured by Toto Kasei Co., Ltd.), 2 parts by mass of curing agent Amicure PN23 (manufactured by Ajinomoto Fine Techno Co., Ltd.), 0.8 parts by mass of triethanolamine citrate salt Mix and mix uniformly using a disper.

  By using the obtained paste-like thermosetting resin composition, solder was supplied by screen printing to the Au-plated pad portion on the FR-4 substrate by an ordinary method. The supply thickness of the paste was about 70 μm.

  Then, it processed in 150 degreeC oven for 10 minutes, and observed the external appearance with the microscope. Solder particles were integrated into a spherical shape, and complete two-layer separation surrounded by a resin not containing solder particles was observed. The resin part was also tack-free.

  Further, when the resistance value and the component shear strength of a component mounted with a 0Ω1608 chip resistor and heat-treated in a reflow oven at 150 ° C. max were measured by the same method, they were 3 mΩ and 2.3 Kgf, respectively. .

  Further, the mounting substrate was boiled in water at 100 ° C. for 2 hours and then subjected to the same measurement. As a result, the connection resistance value and the component shear strength were 3 mΩ and 2.0 Kgf, respectively.

These results are also shown in Table 1.
(Example 2)
As a flux component, a salt obtained by heating reaction of 4.5 g (0.05 mol) of oxalic acid and 7.45 g (0.05 mol) of triethanolamine was used. Other than that was carried out similarly to Example 1, and obtained the thermosetting resin composition. Here, the molar ratio of carboxyl group to amino group is 2: 1.

The same evaluation as in Example 1 was performed, and the results are shown in Table 1.
(Example 3)
In Example 2, normal carboxylic acid was used in combination as a flux component, and 0.5 parts by mass of glutaric acid, 0.25 parts by mass of adipic acid, and 0.45 parts by mass of triethanolamine oxalate salt were used. Moreover, the compounding quantity of the liquid epoxy resin was changed to 15.8 mass parts. Other than that was carried out similarly to Example 2, and obtained the thermosetting resin composition.

The same evaluation as in Example 1 was performed, and the results are shown in Table 1.
(Comparative Example 1)
In Example 3, 3 parts by mass of glutaric acid and 1.5 parts by mass of adipic acid were used, the triethanolamine salt of carboxylic acid was not added at all, and the blending amount of the liquid epoxy resin was changed to 12.5 parts by mass. Otherwise, the thermosetting resin composition was obtained in the same manner as in Example 2.

  The same evaluation as in Example 1 was performed, and the results are shown in Table 1.

  In addition, although evaluation of solder cohesion was performed in Tables 1, 5, and 6, all samples were evaluated as ◯, and there were no samples evaluated as Δ and ×.

  From Table 1, in Examples 1 to 3 in which a triethanolamine salt of a carboxylic acid was blended as a flux component, it was possible to mount a component with excellent solder cohesiveness in a batch reflow process and excellent reliability against moisture absorption. .

  In addition, the compounding quantity of the flux component was examined on the basis of the comparative example 1 which used normal carboxylic acid as a flux component. As a result, the results according to Examples 1 to 3 were obtained when the blending amount of the flux component was within the range of 1 to 10 PHR with respect to the thermosetting resin binder.

Moreover, the result according to Examples 1-3 was obtained in the range whose total amount of a thermosetting resin binder and a flux component is 5-30 mass% with respect to the whole quantity of a thermosetting resin composition.
(Examples 4 to 11)
Dicarboxylic acid or tricarboxylic acid and triethanolamine were mixed in the blending amounts shown in Table 2, and heated in a 120 ° C. oil bath for 5 minutes to obtain a salt. All salts were viscous liquids or semi-solids.

Using this salt, the thermosetting resin composition was obtained in the same manner as in Example 1 with the blending amounts shown in Table 3, and the same evaluation as in Example 1 was further performed. The results are shown in Table 5.
(Examples 12 to 13)
Using the oxalate shown in Example 6 in Table 2, the test was performed with the blending amounts shown in Table 4. Other than that obtained the thermosetting resin composition like Example 4-11, and also implemented evaluation similar to Example 1. FIG. The results are shown in Table 5.

As can be seen from Table 5, all of the examples were excellent in solder agglomeration in the batch reflow process, and could be mounted with excellent reliability in moisture absorption.
(Example 14)
When 1.49 g (0.01 mol) of triethanolamine was added to 1.16 g (0.01 mol) of diglycolic anhydride, it reacted exothermically to form an adduct. In order to complete the reaction, the mixture was further stirred for 5 minutes in a 120 ° C. oil bath. This formulation is 1: 0.5 in terms of the molar ratio of carboxyl groups to amino groups. The obtained diglycolic acid triethanolamine adduct was a viscous liquid.

  As the solder particles, those manufactured by Mitsui Mining & Smelting Co., Ltd. (composition: Sn96.5 / Ag3 / Cu0.5, average particle size 15 μm, melting point 218 ° C.) were used.

82 parts by mass of the solder particles, 16.2 parts by mass of liquid epoxy resin YD128 (manufactured by Toto Kasei), 1 part by mass of imidazole compound 2PZCN (manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing agent. 0.8 parts by mass of diglycolic acid triethanolamine adduct was mixed. A thermosetting resin composition was obtained by the same operation as in Example 1. The same evaluation as in Example 1 was carried out at a curing oven temperature and a maximum reflow temperature of 240 ° C. The results are shown in Table 6.
(Example 15)
In Example 14, 1.05 g (0.01 mol) of diethanolamine was used instead of 1.49 g of triethanolamine. Other than that was carried out similarly to Example 14, and obtained the thermosetting resin composition.

The same evaluation as in Example 14 was performed, and the results are shown in Table 6.
(Example 16)
In Example 14, 1.28 g (0.01 mol) of glutaric anhydride was used in place of diglycolic anhydride. Other than that was carried out similarly to Example 14, and obtained the thermosetting resin composition.

The same evaluation as in Example 14 was performed, and the results are shown in Table 6.
(Example 17)
In Example 14, 1.0 g (0.01 mol) of succinic anhydride was used in place of diglycolic anhydride. Other than that was carried out similarly to Example 14, and obtained the thermosetting resin composition.

  The same evaluation as in Example 14 was performed, and the results are shown in Table 6.

From Table 6, Examples 14-17 which used the addition reaction material of carboxylic anhydride and diethanolamines or triethanolamines as a flux component are excellent in the solder cohesiveness in a batch reflow process, and are reliable with respect to moisture absorption. Excellent component mounting was possible.
(Example 18)
A thermosetting flux composition containing no solder particles in Example 1 was prepared. This was evaluated by a 7 mm square, 144 terminal bonding evaluation CSP and its evaluation board.

  This CSP is composed of Sn96.5 / Ag3 / Cu0.5 0.5mmΦ solder balls mounted at a pitch of 0.8mm. By mounting on the evaluation board, 144 terminal solder joints by daisy chain pattern This is a TEG (Test Element Group).

  A small amount of the produced thermosetting flux composition was added to the connection pad portion (0.5 mm square) wired on the evaluation board using a dispenser. Further, the CSP for bonding evaluation was aligned and mounted, and CSP bonding was performed through a solder reflow furnace under the condition of 240 ° C. max. It was confirmed by repeating n = 5 whether all the balls were electrically bonded to the substrate by the daisy chain pattern.

  As a result, it was confirmed that all five were joined. That is, the yield rate was 100%. Further, when the shear fracture strength of CSP was measured by a bond tester, it was 17.2 kgf.

These results are also shown in Table 7.
(Examples 19 to 20)
Also in the case of Examples 2 and 3, the same experiment as in Example 18 was performed, and the mountability evaluation was performed using the thermosetting flux compositions obtained as Examples 19 and 20, respectively. Table 7 shows the yield rate and shear fracture strength in these experiments.
(Comparative Example 2)
In Comparative Example 1, a thermosetting flux composition containing no solder particles was prepared. Using this thermosetting flux composition, an experiment was conducted in the same manner as in Example 18 to evaluate the mountability.

The results of the yield rate and shear fracture strength are shown in Table 7.
(Comparative Example 3)
An experiment was conducted in the same manner as in Example 18 except that a commercially available flux for BGA and CSP was used, and the mountability was evaluated.

  The results of the yield rate and shear fracture strength are shown in Table 7.

From Table 7, in Examples 18-20 which mix | blended the triethanolamine salt of carboxylic acid as a flux component, the component mounting excellent in the reliability with respect to a drop impact etc. was possible. Compared to Comparative Example 2 using carboxylic acid as a flux component and Comparative Example 3 using a commercially available flux, the shear fracture strength was greatly improved.
(Examples 21 to 24)
Also in the case of Examples 14 to 17, the same experiment as in Example 18 was performed, and the mountability evaluation was performed using the thermosetting flux compositions obtained as Examples 2 to 24, respectively. The yield rate and shear fracture strength in these experiments are shown in Table 8.

  From Table 8, Examples 21 to 24, in which an addition reaction product of carboxylic acid anhydride and diethanolamines or triethanolamines was blended as a flux component, could be mounted with excellent reliability against dropping impacts. It was.

Claims (10)

  A thermosetting resin composition containing solder particles, a thermosetting resin binder, and a flux component, wherein the flux component contains a salt of dicarboxylic acid or tricarboxylic acid and diethanolamine or triethanolamine. A thermosetting resin composition.   The dicarboxylic acid or tricarboxylic acid is at least one selected from adipic acid, glutaric acid, diglycolic acid, propanetricarboxylic acid, citric acid, tartaric acid, oxalic acid, and succinic acid. The thermosetting resin composition as described.   In the thermosetting resin composition containing solder particles, a thermosetting resin binder, and a flux component, the flux component contains an addition reaction product of a carboxylic acid anhydride and diethanolamines or triethanolamines. A thermosetting resin composition.   4. The thermosetting resin composition according to claim 3, wherein the carboxylic acid anhydride is at least one selected from glutaric acid anhydride, diglycolic acid anhydride, and succinic acid anhydride.   The thermosetting resin composition according to any one of claims 1 to 4, wherein a content of the flux component is 1 to 10 PHR with respect to the thermosetting resin binder.   The thermosetting resin composition according to any one of claims 1 to 5, wherein the thermosetting resin binder is an epoxy resin composition.   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 6.   A thermosetting flux composition used as a flux for conductive connection of solder balls or solder bumps, comprising a thermosetting resin binder and a flux component, and as the flux component, dicarboxylic acid or tricarboxylic acid and diethanolamines or A flux composition comprising a salt with triethanolamines.   A thermosetting flux composition used as a flux for conductive connection of solder balls or solder bumps, comprising a thermosetting resin binder and a flux component, and the flux component includes a carboxylic acid anhydride and diethanolamines or A flux composition comprising an addition reaction product with ethanolamines.   A flux composition according to claim 8 or 9 is used as a solder ball or solder bump flux, and the semiconductor component terminal and the circuit board electrode are joined by the solder ball or solder bump. A featured semiconductor device.