JP2009158712A - Adhesive for electronic parts - Google Patents

Abstract

An electronic component that prevents warping of an electronic component, has excellent adhesion reliability, can be suitably used for a coating method using a jet dispensing apparatus, and can be applied precisely. Provide adhesive.
SOLUTION: A specific N group-containing 3-sensitive epoxy compound (A) is 20 to 60% by weight, and an alkyl group, alkenyl group or aralkyl group-containing succinic anhydride compound (C) having a carbon number of 11 to 30 is 30 to 30% by weight. An adhesive for electronic parts containing 60% by weight and a curing accelerator.
[Selection figure] None

Description

The present invention prevents electronic parts from warping and the like, is extremely excellent in adhesion reliability, can be suitably used in a coating method using a jet dispensing apparatus, and can be applied precisely. Relates to adhesives.

In recent years, there is an increasing demand for miniaturization of electrical components such as semiconductor chips. For example, semiconductor chips are becoming thinner. Accordingly, when the semiconductor chip and the substrate are bonded via an adhesive, the problem of warping generated in the semiconductor chip has become an increasingly important issue.
The problem of warping that occurs in this semiconductor chip is the temperature dependence of the elongation rate between the semiconductor chip and the substrate in the process of cooling from the temperature at which the adhesive bonding between the semiconductor chip and the substrate is cured to room temperature. It is considered that the stress caused by the difference is a major factor.

In order to solve such a problem, for example, it is considered that an adhesive that bonds between a semiconductor chip and a substrate is used to relieve a stress caused by a difference in temperature dependence of the elongation rate between the semiconductor chip and the substrate.
Here, in order to relieve the stress caused by the difference in temperature dependence of the elongation rate between the semiconductor chip and the substrate, the adhesive that bonds between the semiconductor chip and the substrate is the storage modulus of the cured product at room temperature. Is required to be 4 GPa or less. However, a general polymer compound satisfying this condition has a storage elastic modulus of about 40 MPa or less at around 175 ° C., and an adhesive composed of such a polymer compound bonds the semiconductor chip and the substrate. Then, it is said that a wire bonding process cannot be performed (for example, refer patent document 1).

On the other hand, as a method for maintaining the storage elastic modulus at room temperature at 4 GPa or lower and the storage elastic modulus at 175 ° C. to exceed 40 MPa, the acrylic resin and the epoxy compound are phase-separated, and further in these resins Discloses a method of highly filling a filler (for example, see Non-Patent Document 1).
However, in such a method, since the filler is highly filled, the adhesive strength of the adhesive is low, and a problem arises in the adhesion reliability of electrical parts such as semiconductor chips.

In recent years, adhesives for electronic parts have been strongly demanded for a degree of freedom in selecting a coating method. However, in the case of a conventionally known adhesive, for example, when a coating method using a jet dispensing apparatus is used, there is a problem such as the occurrence of liquid dripping at the nozzle portion, which meets the demand for a variety of coating methods. Things were not realized.

Further, in recent years, with the increasing needs for downsizing electronic components, there is an increasing demand for precision coating properties for adhesives for electronic components. However, when a conventionally known adhesive, for example, an adhesive that is highly filled with a filler as described above is used, the filler is agglomerated and the nozzle is clogged during application, so that it is difficult to apply the adhesive little by little. Therefore, there was a problem that it could not be applied precisely.
JP 2005-183788 A Hitachi Chemical Technical Report No. 47 (2006-7)

In view of the above situation, the present invention prevents the occurrence of warping of electronic parts, is extremely excellent in adhesion reliability, can be suitably used for a coating method using a jet dispensing apparatus, and performs precise coating. An object of the present invention is to provide an adhesive for electronic parts.

In the present invention, the epoxy compound (A) represented by the following general formula (1) is 20 to 60% by weight and the succinic anhydride compound (C) represented by the following general formula (3) is 30 to 60% by weight. And an adhesive for electronic parts containing a curing accelerator.

In general formula (1), R ₁ represents hydrogen or an alkyl group having 1 to 3 carbon atoms.

In General Formula (3), R ₃ represents an alkyl group, an alkenyl group, or an aralkyl group having 11 to 30 carbon atoms.
The present invention is described in detail below.

As a result of intensive studies, the present inventors have used a predetermined amount of an epoxy compound (A) having a predetermined structure, a predetermined amount of a succinic anhydride compound (C) having a predetermined structure, and a curing accelerator, An adhesive for electronic parts that prevents the occurrence of warping of electronic parts, has excellent adhesion reliability, can be suitably used for a coating method using a jet dispensing apparatus, and can be applied precisely. The present invention has been found, and the present invention has been completed.
This is because, by using the epoxy compound (A) and the succinic anhydride compound (C) in combination, the cured product obtained without using a high filler or the like as in the past, at a low temperature (10 to 50 ° C.). An electronic component having a low storage elastic modulus (1000 to 4000 MPa), a high storage elastic modulus at a high temperature (170 ° C. or higher) (40 MPa or higher), and a glass transition temperature (Tg) in a suitable range (110 to 150 ° C.). This is because an adhesive is obtained. Thus, the obtained cured product is excellent in stress relaxation property in a low temperature region (10 to 50 ° C.), and has very high adhesion reliability without causing bending at the time of wire bonding in a high temperature region (170 ° C. or more). It becomes possible to demonstrate.
Moreover, when an epoxy compound (A), a succinic anhydride compound (C), and a curing accelerator are used in combination, the adhesive for electronic parts of the present invention has a very fast curing speed and can be cured at a low temperature. In the electronic component assembly comprising the adhesive for electronic components of the present invention and the electronic component and substrate bonded via the adhesive for electronic components of the present invention, generation of warpage of the electronic components is extremely effective. It becomes possible to reduce.
Furthermore, since the curing speed of the adhesive for electronic parts of the present invention is very fast as described above, the adhesive for electronic parts of the present invention can be cured before the epoxy compound (A) is volatilized. Therefore, generation of voids can be extremely effectively prevented in the obtained cured product.

The adhesive for electronic components of the present invention contains an epoxy compound (A) represented by the following general formula (1).

In general formula (1), R ₁ represents hydrogen or an alkyl group having 1 to 3 carbon atoms.

By containing such an epoxy compound (A), the storage elastic modulus at high temperature (170 ° C. or higher) of the obtained cured product can be kept high.
Further, when only the epoxy compound (A) is used, the glass transition temperature (Tg) of the obtained cured product becomes too high, and when the electronic component is bonded using the obtained adhesive for electronic components, Although warpage may occur, the glass transition temperature (Tg) of the cured product obtained by using the succinic anhydride compound (C) and the epoxy compound (A) described below in combination is 110 to 150 ° C. It becomes possible to control within a suitable range. Thus, it becomes possible to prevent generation | occurrence | production of the curvature of an electronic component by setting the glass transition temperature (Tg) of the hardened | cured material to 110-150 degreeC.
Furthermore, the epoxy compound (A) is cured extremely quickly by using a succinic anhydride compound (C) described later and a curing accelerator in combination. When the curing speed is high, the epoxy compound (A) is cured before it volatilizes, so that the generation of voids in the resulting cured product can be extremely effectively reduced.

Since the epoxy compound (A) has a low viscosity, the adhesive for electronic parts of the present invention has a relatively low viscosity, is excellent in coating properties, and can be applied to various coating methods. Among these, it can be suitably used for a jet dispensing apparatus.

It does not specifically limit as a commercial item of the said epoxy compound (A), For example, EP3950S, EP3900S (above, all are the products made from ADEKA) etc. are mentioned.

The lower limit of the amount of the epoxy compound (A) is 20% by weight, and the upper limit is 60% by weight. If it is less than 20% by weight, the storage modulus of the resulting cured product at high temperatures may not be sufficiently high, and the viscosity of the resulting adhesive for electronic components may not be sufficiently low. If it exceeds 60% by weight, unreacted epoxy groups remain, which may adversely affect the adhesion reliability of the resulting electronic component assembly. A preferred lower limit is 30% by weight, a preferred upper limit is 50% by weight, and a more preferred upper limit is 40% by weight.

The adhesive for electronic components of the present invention preferably contains an epoxy compound (B) represented by the following general formula (2).

In General Formula (2), R ₂ represents hydrogen or an alkyl group having 1 to 3 carbon atoms.

Such an epoxy compound (B) can be used very suitably for a coating method using a jet dispensing apparatus because its viscosity drops sharply when heated.
In addition, it is thought that the viscosity of the epoxy compound (B) suddenly drops due to heating because the epoxy compound (B) has crystallinity at room temperature, but crystallinity collapses due to heating.

When the epoxy compound (B) is used in combination with the epoxy compound (A), the resulting adhesive for electronic components can have a low viscosity at room temperature, and can also have a low viscosity at high temperature. Thus, excellent dispensing properties, bonding properties, and adhesion reliability can be obtained.
Furthermore, the said epoxy compound (B) hardens | cures very rapidly by using together with the succinic anhydride compound (C) mentioned later similarly to the said epoxy compound (A). Therefore, compared with the case where other reactive diluents are blended, generation of voids can be extremely effectively reduced in the obtained cured product.

It does not specifically limit as a commercial item of the said epoxy compound (B), For example, EX-201 (made by Nagase ChemteX Corporation) etc. are mentioned.

Although it does not specifically limit as a compounding quantity of the said epoxy compound (B), A preferable minimum is 5 weight% and a preferable upper limit is 40 weight%. If it is less than 5% by weight, the viscosity of the resulting adhesive for electronic parts may not be sufficiently low, and the storage elastic modulus of the cured product at high temperatures may not be sufficiently high. If it exceeds 40% by weight, warpage of the electronic component may be increased in the obtained electronic component assembly. A more preferred lower limit is 10% by weight, and a more preferred upper limit is 30% by weight.

The adhesive for electronic components of the present invention may further contain a high molecular weight polymer having an epoxy group (hereinafter also simply referred to as a high molecular weight polymer).
The high molecular weight polymer having an epoxy group is not particularly limited. For example, epoxy-modified polyethylene glycol, epoxy-modified polypropylene glycol, epoxy group-containing acrylic rubber, epoxy group-containing butadiene rubber, bisphenol type high molecular weight epoxy resin, epoxy group-containing phenoxy Examples thereof include an acrylic polymer compound having an epoxy group such as a resin, an epoxy group-containing (meth) acrylic resin, an epoxy group-containing urethane resin, and an epoxy group-containing polyester resin, and an epoxy-terminated NBR resin. These high molecular weight polymers having an epoxy group may be used alone or in combination.

Although it does not specifically limit as a compounding quantity of the high molecular weight polymer which has the said epoxy group, A preferable upper limit is 30 weight%. When it exceeds 30% by weight, a glass transition temperature, a storage elastic modulus, and the like in a desired range may not be achieved for the obtained cured product.

The adhesive for electronic parts of the present invention contains a succinic anhydride compound (C) represented by the following general formula (3) (hereinafter also simply referred to as succinic anhydride compound (C)).

In General Formula (3), R ₃ represents an alkyl group, an alkenyl group, or an aralkyl group having 11 to 30 carbon atoms.

The succinic anhydride compound (C) plays a role as a curing agent.
Further, R ₃ in which the succinic anhydride compound (C) has, in the cured product obtained, exhibits flexibility. That is, when it consists only of the said epoxy compound (A) and the said epoxy compound (B), when it becomes a hard hardened | cured material, when the said succinic anhydride compound (C) is used, the said succinic anhydride compound (C) will become Since the flexible skeleton possessed by the side chain is added, the obtained cured product can exhibit flexibility as a whole. In this way, a relatively low elastic modulus at room temperature can be ensured.

In general, various curing agents other than the succinic anhydride compound (C) can be considered, but when only a curing agent other than the acid anhydride is used, the resulting cured product has a high storage elastic modulus in a high temperature region. However, since the storage elastic modulus at room temperature becomes too high, stress relaxation cannot be obtained, and cracks, warpage, etc. may occur under a thermal cycle.
The adhesive for electronic parts of the present invention can be used as a curing agent even if a compound having the same flexible skeleton in the side chain of the acid anhydride is not necessarily the same compound as the succinic anhydride compound (C). It can be expected to obtain the same effect as the agent.
Such a compound having a flexible skeleton in the side chain of the acid anhydride is not particularly limited, and examples thereof include, for example, an alkyl group having 10 to 16 carbon atoms, an alkenyl group having 10 to 16 carbon atoms, and 10 to 10 carbon atoms. And acid anhydrides having 16 aralkyl groups and the like.

Furthermore, since the succinic anhydride compound (C) has a very high curing speed when used in combination with the epoxy compound (A) and / or the epoxy compound (B) and a curing accelerator, The generation of voids can be extremely effectively reduced, and the occurrence of warping of electronic components can be extremely effectively reduced in the obtained electronic component assembly.

The succinic anhydride compound (C) is not particularly limited, and examples thereof include tetrapropenyl succinic anhydride.

The blending amount of the succinic anhydride compound (C) has a lower limit of 20% by weight and an upper limit of 60% by weight. If it is less than 20% by weight, sufficient flexibility may not be imparted. If it exceeds 60% by weight, adhesion reliability may be lowered due to the presence of an unreacted curing agent. A preferred lower limit is 25% by weight, a more preferred lower limit is 30% by weight, a preferred upper limit is 50% by weight, and a more preferred upper limit is 40% by weight. Moreover, the said acid anhydride may be used independently and may be used together with another acid anhydride. When used in combination with other acid anhydrides, the acid anhydride is preferably contained in an amount of 40 to 80% by weight of the whole acid anhydride.

The adhesive for electronic components of the present invention further contains a curing accelerator.
The curing accelerator is not particularly limited, and examples thereof include imidazole-based curing accelerators and tertiary amine-based curing accelerators. Among them, a reaction system for adjusting the curing speed and the physical properties of the cured product. Therefore, an imidazole curing accelerator is preferably used. These hardening accelerators may be used independently and may use 2 or more types together.
The imidazole curing accelerator is not particularly limited, and examples thereof include 1-cyanoethyl-2-phenylimidazole in which the 1-position of imidazole is protected with a cyanoethyl group, and those whose basicity is protected with isocyanuric acid (trade name “2MA- OK ”, manufactured by Shikoku Kasei Kogyo Co., Ltd.). These imidazole type hardening accelerators may be used independently and may use 2 or more types together.

As for the said hardening accelerator, the minimum with a preferable melting | fusing point is 120 degreeC. By setting the temperature to 120 ° C. or higher, when the electronic component adhesive of the present invention is heated, gelation is suppressed, and the electronic components can be suitably joined and the distance between the electronic components can be adjusted appropriately. Moreover, it is preferable that any one of an acid anhydride agent and a hardening accelerator is a powder.

Examples of the curing accelerator having a melting point of 120 ° C. or higher include 2MZ, 2MZ-P, 2PZ, 2PZ-PW, 2P4MZ, C11Z-CNS, 2PZ-CNS, 2PZCNS-PW, 2MZ-A, 2MZA-PW, and C11Z. -A, 2E4MZ-A, 2MA-OK, 2MAOK-PW, 2PZ-OK, 2MZ-OK, 2PHZ, 2PHZ-PW, 2P4MHZ, 2P4MHZ-PW, 2E4MZ · BIS, VT, VT-OK, MAVT, MAVT-OK (Above, manufactured by Shikoku Kasei Kogyo Co., Ltd.). In particular, a curing accelerator that is stable up to 130 ° C. and activated at 135 to 200 ° C. is preferable. Among those described above, 2MA-OK and 2MAOK-PW are preferable. When these curing accelerators are used, it is possible to achieve both storage stability, stability against heat during the process, and rapid curability.
When using the said acid anhydride and a hardening accelerator together, it is preferable that the compounding quantity of an acid anhydride shall be below theoretically required equivalent with respect to the epoxy group contained in the epoxy compound mentioned above. If the blending amount of the acid anhydride exceeds the theoretically required equivalent, chlorine ions may be easily eluted by moisture after curing. That is, if the curing agent is excessive, for example, when the elution component is extracted with hot water from the cured product of the adhesive for electronic components of the present invention, the pH of the extracted water becomes about 4 to 5, and thus the above-described case. Large amounts of chloride ions may elute from epoxy compounds. Accordingly, it is preferable that the pH of pure water after 1 g of the cured product of the adhesive for electronic parts of the present invention is immersed in 10 g of pure water at 100 ° C. for 2 hours is 6-8, and the pH is 6.5-7. .5 is more preferable.

The amount of the curing accelerator is not particularly limited, and the epoxy compound (when the epoxy compound (A) and the epoxy compound (B) are contained, the epoxy compound (A) and the epoxy compound are included). (A total with (B)) A preferable minimum is 1 weight part with respect to 100 weight part, and a preferable upper limit is 10 weight part.

The adhesive for electronic parts of the present invention further contains spacer particles having an average particle diameter of 2 to 200 μm, a CV value of 10% or less, and a K value of 980 to 10000 N / mm ^2. Is preferred.
By containing such spacer particles, for example, when two or more semiconductor chips are laminated using the adhesive for electronic components of the present invention, each semiconductor chip is interposed via the adhesive for electronic components of the present invention. By adhering to each other, it is possible to keep the distance between the semiconductor chips constant.

The spacer particles can be selected from those having an average particle size such that a desired distance between electronic components can be achieved. The preferable lower limit of the average particle size is 2 μm, and the preferable upper limit is 200 μm. If it is less than 2 μm, it may be difficult to reduce the distance between the electronic components to the particle diameter of the spacer resin particles. If it exceeds 200 μm, the interval between the electronic components may become larger than necessary. A more preferable lower limit is 9 μm, and a more preferable upper limit is 50 μm.

The average particle size of the spacer particles is preferably 1.2 times or more the average particle size of the solid component to be blended in addition to the spacer particles. If it is less than 1.2 times, it may be difficult to reliably reduce the distance between the electronic components to about the particle diameter of the spacer resin particles. More preferably, it is 1.1 times or more.

The spacer particles preferably have a standard deviation of the particle size distribution of 10% or less of the average particle size of the spacer resin particles. By setting it to 10% or less, when electronic components such as a semiconductor chip are stacked, they can be stacked more stably and horizontally.

The spacer particles preferably have a CV value with an upper limit of 10%. If it exceeds 10%, there is a large variation in the particle diameter, so that it is difficult to keep the distance between the electronic components constant, and the function as the spacer resin particles may not be sufficiently achieved. A more preferable upper limit is 6%, and a further preferable upper limit is 4%.
In addition, in this specification, CV value is a numerical value calculated | required by following formula (1).
CV value (%) = (σ2 / Dn2) × 100 (1)
In the above formula (1), σ2 represents the standard deviation of the particle diameter, and Dn2 represents the number average particle diameter.

The spacer particles have a preferable lower limit of K value of 980 N / mm ² and a preferable upper limit of 10,000 N / mm ² .
In addition, in this specification, K value is a numerical value calculated | required by following formula (2).
^{K = (3 / √2) ·} F · S -3/2 · R -1/2 (2)
In the above formula (2), F and S represent the load value (kgf) and compression displacement (mm) in 10% compression deformation of the spacer particles, respectively, and R represents the radius (mm) of the spacer.

The K value can be measured by the following measuring method.
First, after spraying spacer resin particles on a steel plate having a smooth surface, one spacer resin particle is selected from the spacer resin particles, and a spacer is formed on a smooth end surface of a diamond cylinder having a diameter of 50 μm using a micro compression tester. Compress the resin particles. At this time, the compression load is electrically detected as an electromagnetic force, and the compression displacement is electrically detected as a displacement by the operating transformer. Then, a load value and a compression displacement in 10% compression deformation are obtained from the obtained compression displacement-load relationship, and a K value is calculated from the obtained result.

The preferable lower limit of the compression recovery rate when the spacer particles are released from the compression deformation state at 20 ° C. and 10% is 20%. When spacer resin particles having such a compression recovery rate are used, even if spacer resin particles larger than the average particle diameter exist between the laminated electronic components, the shape is recovered by compressive deformation and used as a gap adjusting material. Can work. Therefore, electronic components can be horizontally stacked at a more stable and constant interval.
The compression recovery rate can be measured by the following measurement method.
The compression displacement is electrically detected as the displacement by the operating transformer by the same method as in the measurement of the K value, and the load is reduced after compression to the reverse load value. The relationship between the load and the compression displacement at that time taking measurement. The compression recovery rate is calculated from the obtained measurement result. However, the end point in the removal load is not a load value of zero but an origin load value of 0.1 g or more.

The spacer particles are preferably resin particles or organic-inorganic hybrid particles.
The material of the spacer resin particles is not particularly limited. For example, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide , Polysulfone, polyphenylene oxide, polyacetal and the like. Among these, it is preferable to use a crosslinked resin because it is easy to adjust the hardness and recovery rate of the spacer resin particles and can improve the heat resistance.

The cross-linked resin is not particularly limited. For example, epoxy resin, phenol resin, melamine resin, unsaturated polyester resin, divinylbenzene polymer, divinylbenzene-styrene copolymer, divinylbenzene-acrylate copolymer, diallyl Examples thereof include a resin having a network structure such as a phthalate polymer, a triallyl isocyanurate polymer, and a benzoguanamine polymer. Of these, divinylbenzene polymer, divinylbenzene-styrene copolymer, divinylbenzene- (meth) acrylate copolymer, diallyl phthalate polymer, and the like are preferable. When these are used, the resistance to a heat treatment process such as a curing process or a solder reflow process is excellent after the chip is bonded.

The organic-inorganic hybrid spacer particles are not particularly limited, and particles containing alkoxysilane as a main component can be used. For example, by hydrolytic polycondensation of alkoxysilane in accordance with the description in Japanese Patent No. 2698541. I can get it.

The spacer particles are preferably spherical. The preferable upper limit of the aspect ratio of the spacer resin particles is 1.1. By setting the aspect ratio to 1.1 or less, when electronic components are stacked, the interval between the electronic components can be kept stable and constant. In the present specification, the aspect ratio means the ratio of the length of the major axis to the length of the minor axis (the value obtained by dividing the length of the major axis by the length of the minor axis) with respect to the major axis and minor axis of the particle. . The closer the aspect ratio value is to 1, the closer the shape of the spacer resin particles is to a true sphere.

The preferable lower limit of the blending amount of the spacer particles is 0.01% by weight, and the preferable upper limit is 5% by weight. When the amount is less than 0.01% by weight, the distance between the electronic components may not be stably maintained when used for manufacturing the electronic component laminate. As a result, the function may be deteriorated.
Moreover, when containing the solid component which has a diameter more than the average particle diameter of the said spacer particle other than the said spacer particle, the upper limit with the preferable compounding quantity of such a solid component is 1 weight%. The melting point of the solid component is preferably not higher than the curing temperature.
Furthermore, the maximum particle size of the solid component is preferably 1.1 to 1.5 times, more preferably 1.1 to 1.2 times the average particle size of the spacer particles.

The adhesive for electronic components of the present invention may further contain an inorganic ion exchanger as necessary. Among the inorganic ion exchangers, examples of commercially available products include IXE series (manufactured by Toagosei Co., Ltd.). The preferable lower limit of the amount of the inorganic ion exchanger is 1% by weight, and the preferable upper limit is 10% by weight.
The adhesive for electronic components of the present invention may further contain various additives such as a bleed inhibitor; and an adhesion promoter such as an imidazole silane coupling agent, if necessary.
In addition, it is preferable that the adhesive for electronic components of this invention does not contain a solvent. When the adhesive for electronic parts of the present invention contains a solvent, voids may be generated during curing for joining the electronic parts, resulting in lack of reliability.

The adhesive for electronic components of the present invention has a preferred lower limit of 1 Pa · s and a preferred upper limit of 100 Pa · s, measured using an E-type viscometer at 25 ° C. and 10 rpm. By having such a viscosity, it becomes possible to cope with diversification of coating methods such as a jet dispensing apparatus. If it is less than 1 Pa · s, the shape of the adhesive coating layer after coating by the jet dispensing apparatus may not be suitably maintained at room temperature. If it exceeds 100 Pa · s, the adhesive for electronic parts of the present invention may accumulate at the tip of the nozzle during application by a jet dispensing apparatus, and may not be discharged.

The adhesive for electronic components of the present invention has a preferred lower limit of 0.1 Pa · s and a preferred upper limit of 1 Pa · s measured with an E-type viscometer at 80 ° C. and 10 rpm. By having such a viscosity, it becomes possible to cope with diversification of coating methods such as a jet dispensing apparatus. If it is less than 0.1 Pa · s, even if the viscosity characteristics at room temperature satisfy the above-mentioned range, the adhesive with reduced viscosity wets and spreads at the nozzle tip, and the applicability by the jet dispensing device decreases. There is. If it exceeds 1 Pa · s, a large amount of adhesive adheres to the vicinity of the nozzle discharge port, and the continuous discharge property may deteriorate.

When the adhesive for electronic components of the present invention is a cured product, the preferable lower limit of the glass transition temperature (Tg) of the cured product is 110 ° C., and the preferable upper limit is 150 ° C. By having a glass transition temperature in this range, it is possible to prevent warping of the electronic component in the electronic component assembly obtained by bonding the electronic component and the substrate. If it is less than 110 ° C, the amount of extracted chlorine at 20 ° C may be extracted in large amounts. If the temperature exceeds 150 ° C., the warping amount of the electronic component may increase.
In this specification, the glass transition temperature (Tg) can be measured from an endothermic curve obtained by heating the sample at a rate of 20 ° C./min using DSC.

When the adhesive for electronic parts of the present invention is a cured product, the preferable lower limit of the storage elastic modulus at 10 to 50 ° C. of the cured product is 1000 MPa, and the preferable upper limit is 4000 MPa. By having the storage elastic modulus in such a temperature region, when the electronic component such as a semiconductor chip and the substrate are bonded using the adhesive for electronic components of the present invention, it has moderate flexibility in the normal temperature region. Thus, the adhesion between the electronic component such as a semiconductor chip and the substrate is excellent, and the generation of a large warp in the electronic component such as the semiconductor chip adhered to the substrate can be prevented. If it is less than 1000 MPa, a large amount of extracted chlorine may be extracted. When it exceeds 4000 MPa, the adhesive force becomes insufficient, and peeling or the like may occur after the electronic component and the substrate are bonded.

When the adhesive for electronic parts of the present invention is a cured product, the preferable minimum storage elastic modulus at 170 ° C. or higher of the cured product is 40 MPa or more. By having the minimum storage elastic modulus in such a temperature region, after performing adhesion between the electronic component such as a semiconductor chip and the substrate using the adhesive for electronic components of the present invention, the cured product does not bend, Wire bonding processing can be performed. If the pressure is less than 40 MPa, the cured product may be bent when performing the wire bonding process, and the wire bonding process may not be performed.

The diameter when the adhesive for electronic components of the present invention is an adhesive layer having a thickness of 10 μm and the cured product obtained by curing the adhesive layer at 170 ° C. for 15 minutes is exposed to a temperature condition of 260 ° C. for 10 seconds. A preferable upper limit of the void generation rate of 100 μm or less is 1 piece / mm ² . When the incidence of voids in the cured product is more than 1 piece / mm ² , when the electronic components are bonded using the adhesive for electronic components of the present invention, the connection reliability between the electronic components is May be insufficient.

The method for producing the adhesive for electronic parts of the present invention is not particularly limited. For example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, or a three-roller, at room temperature, the above The method etc. which mix each predetermined amount, such as a polyfunctional epoxy compound and the said acid anhydride, etc. are mentioned.

By using the adhesive for electronic components of the present invention, an electronic component assembly can be produced. Specifically, for example, after the adhesive for electronic components of the present invention is applied between the electronic component and the substrate, the adhesive for electronic components of the present invention is cured by curing the adhesive for electronic components of the present invention. It is possible to manufacture an electronic component assembly comprising an agent, an electronic component bonded through the electronic component adhesive of the present invention, and a base material.

Although it does not specifically limit as a method of apply | coating the adhesive agent for electronic components of this invention between an electronic component and a base material, For example, the apply | coating method using a jet dispensing apparatus is preferable. By using a jet dispensing device, it is possible to apply a dot-like adhesive in a short time, have excellent quantification of the amount of adhesive to be discharged, and can be applied even if there is a step on the substrate surface. Will have.

A method for producing the electronic component assembly using the jet dispensing apparatus is not particularly limited. For example, the present invention in which the adhesive for electronic components of the present invention is applied to a substrate and applied onto the substrate. The electronic component is pressed on the electronic component adhesive, and the base material and the electronic component are bonded together via the electronic component adhesive of the present invention, and then the electronic component adhesive of the present invention is heated. And a curing method.
Thus, the step of applying the adhesive for electronic components of the present invention to the substrate, and pressing the electronic component on the adhesive for electronic components of the present invention applied on the substrate, the electronic component of the present invention The method for producing an electronic component assembly comprising a step of bonding the base material and the electronic component through an adhesive for heating, and a step of heating and curing the adhesive for electronic component of the present invention is also disclosed in the present invention. One.

By using the method for manufacturing an electronic component assembly of the present invention or the electronic component adhesive of the present invention, an electronic component such as a semiconductor chip and a substrate are bonded to each other to manufacture the electronic component assembly. Can significantly improve the warpage. Specifically, for example, the adhesive for electronic components of the present invention is applied to a thickness of 10 μm between a 10 mm × 10 mm, 80 μm thick semiconductor chip and a 20 mm × 20 mm, 170 μm thick Taisho Electronics substrate. When heated at 100 ° C. for 40 minutes and then at 170 ° C. for 15 minutes, the adhesive for electronic components of the present invention is cured, and the warpage of the semiconductor chip at that time is suppressed to about 100 μm.

By using the method for producing an electronic component assembly of the present invention or the electronic component adhesive of the present invention, an electronic component such as a semiconductor chip and a substrate are bonded to each other to produce an electronic component assembly. The component adhesive can also perform extremely precise drawing without causing variations in the application amount and application state.
In general, when a conventionally known adhesive is used, the application amount cannot be strictly controlled as the application amount of the adhesive becomes small, and the application amount and the application state vary. Specifically, for example, in the case of using a jet dispensing apparatus, if the amount of adhesive to be discharged is reduced, the amount of adhesive that is actually applied varies.
On the other hand, when the method for manufacturing an electronic component assembly of the present invention or the adhesive for electronic components of the present invention is used, even if the coating amount is small, the coating amount and the coating state do not vary. By using the method for producing an electronic component joined body of the invention or the electronic component adhesive of the invention, it is possible to draw a precise drawing such as a very thin line.
Specifically, even when the coating amount is as small as 0.1 mg, the variation amount with respect to the average coating amount can be ± 0.01 mg (3σ) in the obtained normal distribution. Since the average coating amount is ± 0.01 mg (3σ), it has a very small variation. By using the method for manufacturing an electronic component joined body of the present invention or the adhesive for electronic components of the present invention, precision such as very thin lines can be obtained. Can be drawn.
In the present specification, σ represents a standard deviation.

ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of the curvature of an electronic component, etc. can be prevented, it is excellent in adhesion reliability, can be used suitably for the coating method using a jet dispensing apparatus, and precise coating is possible. An adhesive for electronic parts can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited only to these examples.

(Examples 1-2, Comparative Examples 1-5)
According to the composition of the following Table 1, the materials shown below were stirred and mixed using a homodisper to prepare adhesives for electronic parts according to Examples 1-2 and Comparative Examples 1-5.
(1) Polyfunctional epoxy compound (A)
Trifunctional glycidyl aniline type epoxy (EP-3900S, manufactured by Adeka)
Trifunctional dicyclopentadiene type epoxy (HP-7200H, manufactured by Dainippon Ink, Inc.)
(2) Epoxy compound (B)
Resorcinol type epoxy (EX-201, manufactured by Nagase ChemteX Corporation)
Bisphenol F type epoxy (YSLV-80XY, manufactured by Tohto Kasei Co., Ltd.)
(3) Other high molecular weight polymers having epoxy groups (high molecular weight polymers)
Acrylic modified epoxy (CP-30, manufactured by NOF Corporation)
(4) Curing agent dodecenyl succinic anhydride (DDSA, manufactured by Shin Nippon Rika Co., Ltd.)
Methylbutenyltetrahydrophthalic anhydride (YH-306, manufactured by Japan Epoxy Resin Co., Ltd.)
(5) Curing accelerator Imidazole-based curing accelerator (2MA-OK, manufactured by Shikoku Kasei Co., Ltd.)
(6) Thickener surface hydrophobized fumed silica (PM-20L, manufactured by Tokuyama Corporation)

(Evaluation)
The following evaluation was performed about the adhesive agent for electronic components prepared in Examples 1-2 and Comparative Examples 1-5. The results are shown in Table 1.

(1) Adhesive for electronic parts (1-1) Viscosity measurement E-type viscosity measuring device (trade name: VISCOMETER TV-22, manufactured by TOKI SANGYO CO. LTD, rotor used: φ15 mm, set temperature: 25 ° C. and 80 ° C. ) And the viscosity at a rotation speed of 10 rpm was measured.

(1-2) Suitability for jet dispensing Jet dispensing suitability was evaluated using a jet dispensing apparatus (DJ-9000, manufactured by Asymtec Corp.). The parts used were a nozzle (No. 4, 100 μm diameter), a valve (C-03, 380 μm), and a needle assembly (No. 16, 2.4 mm). The discharge conditions are a nozzle temperature of 50 ° C. or 80 ° C., a stroke of 780 μm, a hydraulic pressure of 1000 kPa, a valve pressure of 558 kPa, a valve on time of 5 ms, a valve off time of 5 ms, and a nozzle height of 1.0 mm.
The case where the nozzle temperature was 50 ° C. or 80 ° C. and the discharge could be continued for 30 minutes was indicated as “◯”, and the case where the discharge stopped by 30 minutes was indicated as “X”.

(1-3) Curing speed The curing speed of the adhesive for bonding a semiconductor chip was evaluated by gel time at 170 ° C. The gel time is measured by placing a resin paste about 1 mm thick in an aluminum cup (diameter: 2 cm, thickness: about 50 μm) and placing it in an oven at 170 ° C. (SPHH-101, manufactured by ESPEC) so that the resin paste does not string. Time was defined as gel time. Prior to the measurement, preheating was performed for 60 minutes.

(2) Cured product (2-1) Measurement of glass transition temperature (Tg) Using viscoelasticity measuring machine manufactured by IT Measurement Control Co., Ltd., adhesives for electronic parts prepared in Examples and Comparative Examples were 170 ° C., 15 The temperature at 25 ° C. and 175 ° C. of the cured product cured in minutes, the temperature at the peak of Tan δ when measured at a heating rate of 5 ° C./min, tension, grip width of 24 mm, and 10 Hz is the glass transition point. did.

(2-2) Measurement of storage elastic modulus Using a viscoelasticity measuring machine manufactured by IT Measurement Control Co., Ltd., a cured product obtained by curing the adhesive for electronic parts prepared in Examples and Comparative Examples at 170 ° C. for 15 minutes. The storage elastic modulus at 25 ° C. and 175 ° C. was measured at a heating rate of 5 ° C./min, pulling, grip width of 24 mm, and 10 Hz.
In addition, in FIG. 1, the graph which shows the relationship between the storage elastic modulus and temperature of the hardened | cured material of the adhesive agent for electronic components each prepared in Example 1, the comparative example 1, and the comparative example 3 is shown.

(2-3) Measurement of voids Using the obtained adhesive for electronic components, a silicon chip and a substrate (manufactured by Daisho Electronics Co., Ltd.) were joined, and the adhesive layer (with a resin thickness of 10 um) was placed at 170 ° C. for 15 minutes. The cured product is exposed to a temperature condition of 260 ° C. for 10 seconds, and then used with an ultrasonic imaging apparatus SAT (Scan Acoustic Tomograph, mi-scope hyper II, manufactured by Hitachi Construction Machinery Finetech Co., Ltd.) The presence or absence of voids between the substrates was observed. A case where the number of voids having a diameter of 100 μm or less was 1 piece / mm ² or less was evaluated as “◯”, and a case where the void was more than that was evaluated as “X”.

(3) Electronic component assembly (3-1) Production of semiconductor chip assembly The obtained adhesive for electronic components was filled into a 10 mL syringe (manufactured by Iwashita Engineering Co., Ltd.), and a precision nozzle (manufactured by Iwashita Engineering Co., Ltd., A nozzle tip diameter of 0.3 mm) is attached, and applied on a glass substrate using a dispenser device (SHOT MASTER300, manufactured by Musashi Engineering Co., Ltd.) with a discharge pressure of 0.4 MPa, a gap between the semiconductor chip and the needle of 200 μm, and a coating amount of 5 mg. did. The application amount was set to (application amount to the outer peripheral portion of the joint portion / application amount to the central portion) = 4.
After coating, a semiconductor chip (chip 1) having 172 110 μm pad openings in a peripheral shape (thickness 80 μm, 10 mm × 10 mm square, mesh pattern, aluminum wiring: thickness 0.7 μm, L / S = 15/15, the thickness of the silicon nitride film on the surface: 1.0 μm) was laminated by pressing at a normal pressure of 0.1 MPa for 5 seconds using a flip chip bonder (DB-100, manufactured by Kasuya Kogyo Co., Ltd.). By heating at 170 ° C. for 15 minutes and curing the adhesive for electronic components, a semiconductor chip joined body was produced.

(3-2) Measurement of warp amount of semiconductor chip The warp amount was measured with a laser displacement meter (LT9010M, KS-1100, manufactured by KEYENCE) along the diagonal line of the semiconductor chip of the manufactured semiconductor chip assembly.

(3-3) Wire Bondability Evaluation Similar to the semiconductor chip assembly, a semiconductor chip (chip 2) (thickness 80 μm, 3 mm × 3 mm square, mesh pattern, aluminum wiring: thickness 0.7 μm, L / L S = 15/15, the thickness of the surface silicon nitride film: 1.0 μm). Thereafter, the laminate was cured at 170 ° C. for 15 minutes. And wire bonding was performed with the wire of diameter 25 micrometers using wire bonder UTC2000 (made by Shinkawa company). The wire was pulled at the wire neck portion, and the one cut at the wire neck was marked with ◯, and the one cut at the joined portion was marked with ×.

(3-4) Evaluation of reflow resistance After the produced semiconductor chip joined body is left in a constant temperature and high humidity oven at 85 ° C. and 85% for 24 hours, an IR in which 230 ° C. or higher is 20 seconds or longer and the maximum temperature is 260 ° C. The reflow furnace was charged three times. After the introduction, the presence or absence of reflow cracks in the semiconductor device was observed with an ultrasonic flaw detector (SAT) and evaluated according to the following criteria.
A: Reflow crack occurrence number 0/30
○: Number of reflow cracks generated 1/30
Δ: Number of reflow cracks generated 2/30
X: Number of reflow cracks generated 3/30

ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of the curvature of an electronic component, etc. can be prevented, it is excellent in adhesion reliability, can be used suitably for the coating method using a jet dispensing apparatus, and precise coating is possible. An adhesive for electronic parts can be provided.

The graph which shows the relationship between the storage elastic modulus and temperature of the hardened | cured material of the adhesive agent for electronic components each adjusted in Example 1, the comparative example 1, and the comparative example 3. FIG.

Claims (9)

Curing acceleration with 20 to 60% by weight of epoxy compound (A) represented by the following general formula (1) and 20 to 50% by weight of succinic anhydride compound (C) represented by the following general formula (3) An adhesive for electronic parts, comprising an agent.

In general formula (1), R ₁ represents hydrogen or an alkyl group having 1 to 3 carbon atoms.

In General Formula (3), R ₃ represents an alkyl group, an alkenyl group, or an aralkyl group having 11 to 30 carbon atoms. Furthermore, 20-60 weight% of epoxy compounds (B) represented by following General formula (2) are contained, The adhesive agent for electronic components of Claim 1 characterized by the above-mentioned.

In General Formula (2), R ₂ represents hydrogen or an alkyl group having 1 to 3 carbon atoms. Furthermore, spacer particles having an average particle diameter of 2 to 200 μm, a CV value of 10% or less, and a K value of 980 to 10000 N / mm ² are contained. Adhesive for electronic parts. 4. The adhesive for electronic parts according to claim 1, wherein the spacer particles are resin particles or organic-inorganic hybrid particles. 5. The adhesive for electronic parts according to claim 1, wherein the viscosity measured at 25 ° C. and 10 rpm using an E-type viscometer is 1 to 100 Pa · s. 6. The adhesive for electronic parts according to claim 1, wherein the viscosity measured at 80 ° C. and 10 rpm using an E-type viscometer is 0.1 to 1 Pa · s. Agent. In the case of a cured product, the cured product has a glass transition temperature (Tg) of 110 to 150 ° C, a storage elastic modulus at 10 to 50 ° C of 1000 to 4000 MPa, and a minimum storage elasticity at 170 ° C or higher. The adhesive for electronic parts according to claim 1, wherein the rate is 40 MPa or more. Applying the adhesive for electronic components according to claim 1, 2, 3, 4, 5, 6 or 7 to a substrate using a jet dispensing apparatus;
Pressing the electronic component onto the adhesive for electronic component applied on the base material, and bonding the base material and the electronic component through the adhesive for electronic component;
And a step of heating and curing the adhesive for electronic components. When the application amount of the adhesive for electronic components according to claim 1, 2, 3, 4, 5, 6 or 7 is 0.1 mg, the variation amount with respect to the average application amount is ± 0.01 mg in the obtained normal distribution. 9. The method of manufacturing an electronic component joined body according to claim 8, wherein (3σ).

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