JP2017066170A - Manufacturing method of electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of an electronic component, with which an out-gas generated when the electronic component is exposed to high temperature is reduced and heat-resistant adhesion reliability is enhanced.SOLUTION: A production method of an electronic component 1 includes: an application step to apply a photocurable adhesive to become an adhesive layer 3 after curing to a surface of a first electronic component body 2 by using an inkjet device; a light irradiation step to make the adhesive irradiated with light so that illuminance becomes 300 mW/cmor more; further, an arrangement step to arrange a second electronic component body 4 on a surface of the adhesive layer 3 opposite to the first electronic component body 2 side while using the adhesive as it is, or going through a second light irradiation step of conducting light irradiation for the second time; and a molding step to mold the laminate by imparting pressure so as to stick the electronic component bodies, in which the adhesive includes a first photo-curable compound having one (meth)acryloyl group, a second photo-curable compound having two or more (meth)acryloyl groups, and a photoinitiator.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electronic component manufacturing method in which an adhesive is applied by an inkjet apparatus.

  For bonding a semiconductor element and a support member such as a substrate, a paste-like adhesive is mainly used as a semiconductor element fixing adhesive.

  In recent years, with the miniaturization of semiconductor elements, the miniaturization of semiconductor packages, and the enhancement of performance, the supporting members used are also required to be miniaturized. In response to such demands, paste-like adhesives have problems such as wetting and spreading and protruding. Moreover, it is difficult to control the thickness with a paste-like adhesive, and as a result, the semiconductor element is tilted, causing problems such as wire bonding defects. For this reason, in recent semiconductor packages, it has become impossible to sufficiently deal with conventional bonding using a paste-like adhesive.

  In recent years, as described in Patent Document 1 below, an adhesive sheet having a film-like adhesive layer has been used.

  In this bonding method using an adhesive sheet, first, an adhesive sheet (adhesive layer) is attached to the back surface of the semiconductor wafer, and a dicing sheet is attached to the other surface of the adhesive layer. Thereafter, by dicing, the semiconductor wafer is separated into pieces with the adhesive layer bonded to obtain a semiconductor element. Next, the semiconductor element with the adhesive layer is picked up and joined to the support member. Then, a semiconductor device is obtained through assembly processes such as wire bonding and sealing.

  However, in the manufacture of a semiconductor device using an adhesive sheet, there is a problem that the adhesive sheet clings to the cutting blade at the time of dicing, so that the cutting performance is lowered, the semiconductor chip is chipped and the yield is lowered. Further, since the supporting member such as the substrate has a step such as a wiring pattern, a void tends to remain in the stepped portion. Voids cause deterioration in reliability.

  Patent Document 2 discloses an adhesive containing a radiation polymerizable compound, a photoinitiator, and a thermosetting resin. When this adhesive is cured, it is heated after being irradiated with light.

  In Patent Document 3 below, an adhesive containing (1) an epoxy resin, (2) a radical curable resin, (3) a photo radical initiator, and (4) a latent epoxy curing agent is disclosed. (4) The latent epoxy curing agent includes: (a) an amine compound represented by a specific formula (I); (b) a polyamine compound having two or more amino groups in the molecule; and (c) an organic polyisocyanate compound. And (d) obtained by reacting an epoxy compound. When this adhesive is cured, it is heated after being irradiated with light.

Japanese Patent Laid-Open No. 3-192178 WO2011 / 058998A1 JP2013-82836A

  In the conventional method for manufacturing an electronic component using an adhesive as described in Patent Documents 2 and 3, the adhesiveness after bonding may be lowered. Further, the conventional method for manufacturing an electronic component has a problem that when exposed to a high temperature, outgas is generated and the peripheral members are contaminated or the adhesive strength is lowered.

  The objective of this invention is providing the manufacturing method of the electronic component which can reduce the outgas when the electronic component obtained is exposed to high temperature, and can improve heat-resistant adhesion reliability.

According to a wide aspect of the present invention, using an inkjet device, a coating step of applying a photocurable adhesive on the surface of the first electronic component main body, and an illuminance of light of 300 mW / cm ² or more There is a light irradiation step of irradiating the adhesive with light, and an arrangement step of disposing a second electronic component main body on the surface of the adhesive opposite to the first electronic component main body side. A first photocurable compound having one (meth) acryloyl group, a second photocurable compound having two or more (meth) acryloyl groups, and a photopolymerization initiator. A method for manufacturing an electronic component is provided.

  In a specific aspect of the method for manufacturing an electronic component according to the present invention, the adhesive has photocurability and thermosetting, the adhesive includes a thermosetting compound and a thermosetting agent, and the electronic The component manufacturing method includes a heating step of heating the adhesive.

  In a specific aspect of the method for manufacturing an electronic component according to the present invention, the adhesive does not include or includes light and a thermosetting compound, and the adhesive does not include the light and the thermosetting compound. Is a total of 100% by weight of the first photocurable compound and the second photocurable compound, and the content of the first photocurable compound is 70% by weight or more and 99.9% by weight or less. When the content of the second photocurable compound is 0.1 wt% or more and 30 wt% or less, and the adhesive contains the light and thermosetting compound, the first photocurable compound In a total of 100% by weight of the photocurable compound, the second photocurable compound, and the light and thermosetting compound, the content of the first photocurable compound is 70% by weight or more and 99.9% by weight. % Or less, and the content of the second photocurable compound is 0.1% by weight or more 30% by weight or less.

  In a specific aspect of the method for manufacturing an electronic component according to the present invention, the adhesive has photocurability and thermosetting, and the adhesive includes light and a thermosetting compound and a thermosetting agent, The manufacturing method of an electronic component includes a heating process for heating the adhesive.

  In a specific aspect of the method for producing an electronic component according to the present invention, the light and thermosetting compound has at least one (meth) acryloyl group and at least one cyclic ether group. Containing sexual compounds.

  On the specific situation with the manufacturing method of the electronic component which concerns on this invention, the said optical and thermosetting compound contains 4-hydroxybutyl acrylate glycidyl ether.

  In a specific aspect of the method for manufacturing an electronic component according to the present invention, the first electronic component body is a semiconductor element or a support member for mounting a semiconductor element, and the second electronic component body is a semiconductor. It is an element, or the first electronic component main body is a semiconductor wafer and the second electronic component main body is a cover glass.

  In a specific aspect of the electronic component manufacturing method according to the present invention, the adhesive has photocurability and thermosetting, and the first electronic component body is a semiconductor element or a support member for mounting a semiconductor element. And the second electronic component main body is a semiconductor element, the light irradiation step is performed after the coating step, the arrangement step is performed after the light irradiation step, and the manufacturing method of the electronic component includes: A heating step of heating the light-irradiated adhesive is provided after the placing step.

  On the specific situation with the manufacturing method of the electronic component which concerns on this invention, the said adhesive agent has photocurability and thermosetting, a said 1st electronic component main body is a semiconductor wafer, and said 2nd The electronic component body is a cover glass, the light irradiation step is performed after the application step, the arrangement step is performed after the light irradiation step, and the manufacturing method of the electronic component is irradiated with light after the arrangement step. A heating step of heating the adhesive; and a cutting step of cutting the laminate of the semiconductor wafer, the adhesive, and the cover glass after the heating step.

In the method for manufacturing an electronic component according to the present invention, an application step of applying a photo-curing adhesive onto the surface of the first electronic component main body using an inkjet device, and an illuminance of light of 300 mW / cm ^2. As described above, the light irradiation step of irradiating the adhesive with light, and the placement step of disposing the second electronic component main body on the surface of the adhesive opposite to the first electronic component main body side. A first photocurable compound having one (meth) acryloyl group, a second photocurable compound having two or more (meth) acryloyl groups, and a photopolymerization initiator. Therefore, the outgas when the obtained electronic component is exposed to a high temperature can be reduced, and the heat-resistant adhesion reliability can be improved.

FIG. 1 is a front sectional view schematically showing an electronic component obtained by a method for manufacturing an electronic component according to an embodiment of the present invention. 2A to 2E are cross-sectional views for explaining each step of the method for manufacturing the electronic component shown in FIG. FIG. 3 is a schematic configuration diagram illustrating an example of an ink jet apparatus used in the method of manufacturing the electronic component illustrated in FIG. FIG. 4 is a schematic configuration diagram illustrating another example of an ink jet apparatus used in the method of manufacturing an electronic component illustrated in FIG. FIG. 5 is a front sectional view schematically showing a modification of the electronic component shown in FIG. FIG. 6 is a front sectional view schematically showing a first modification of the electronic component. FIG. 7 is a front sectional view schematically showing a second modification of the electronic component.

  Hereinafter, the present invention will be described in detail.

In the method for manufacturing an electronic component according to the present invention, an application step of applying a photo-curing adhesive onto the surface of the first electronic component main body using an inkjet device, and an illuminance of light of 300 mW / cm ^2. As described above, the light irradiation step of irradiating the adhesive with light, and the placement step of disposing the second electronic component main body on the surface of the adhesive opposite to the first electronic component main body side. With.

  In the method for manufacturing an electronic component according to the present invention, the adhesive includes a first photocurable compound having one (meth) acryloyl group and a second photocurable resin having two or more (meth) acryloyl groups. A compound and a photopolymerization initiator.

  In the present invention, since the above-described configuration is provided, outgas when the obtained electronic component is exposed to a high temperature can be reduced, and heat-resistant adhesion reliability can be improved. In the present invention, since the adhesive having a specific composition is used and the illuminance of light is set to be extremely high, the above-described effects are effectively exhibited.

From the viewpoint of further suppressing outgas generation and effectively improving heat-resistant adhesion reliability, the illuminance of light in the light irradiation step is preferably 500 mW / cm ² or more. From the viewpoint of further improving the moisture-resistant adhesion reliability and the thermal cycle reliability, the illuminance of light in the light irradiation step is preferably 3000 mW / cm ² or less.

  In addition, the illuminance of the present invention is a value measured by UVI Cure Plus 2 manufactured by Illuminometer Electronic Instruments and Technology.

Note that the illuminance of light has a greater influence on the suppression of outgassing and the improvement of heat-resistant adhesion reliability than the integrated amount of light. Integrated light quantity of the light is preferably 10 mJ / cm ² or more, more preferably 100 mJ / cm ² or higher, preferably 5000 mJ / cm ² or less, more preferably 4000 mJ / cm ² or less.

  The adhesive is preferably applied in a state heated to 50 ° C. or higher and 100 ° C. or lower.

  Since the adhesive is applied using an ink jet apparatus, it is liquid at the time of application, and is generally liquid at 25 ° C. The viscosity at 25 ° C. and 10 rpm of the adhesive is preferably 3 mPa · s or more, more preferably 5 mPa · s or more, still more preferably 160 mPa · s or more, preferably 2000 mPa · s or less, more preferably 1600 mPa · s or less, More preferably, it is 1500 mPa · s or less. From the viewpoint of further increasing the thickness accuracy of the cured adhesive and further preventing voids in the cured adhesive, the viscosity of the adhesive at 25 ° C. and 10 rpm is 160 mPa · s or more and 1600 mPa · s or less. It is particularly preferred that

  The viscosity is measured at 25 ° C. using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K2283.

  From the viewpoint of forming the cured adhesive with higher accuracy and making it harder to generate voids in the cured adhesive, it is preferable to apply the adhesive while circulating the adhesive.

  The ink jet device includes an ink tank that stores the adhesive, a discharge unit that is connected to the ink tank and discharges the adhesive, one end is connected to the discharge unit, and the other end It is preferable to have a circulation flow path portion connected to the ink tank and through which the adhesive flows.

  When the adhesive is applied, after the adhesive is moved from the ink tank to the discharge part in the ink jet apparatus, the adhesive that has not been discharged from the discharge part is moved into the circulation channel part. Is applied to the ink tank while circulating the adhesive. If the adhesive is applied while being circulated, the effects of the present invention can be obtained more effectively. That is, the thickness accuracy of the cured adhesive can be further increased, and voids can be further hardly generated in the cured adhesive.

  In the present invention, a thick adhesive can be formed with high accuracy. In the present invention, even a multi-layered adhesive can be formed finely and with high accuracy.

  Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 is a front sectional view schematically showing an electronic component obtained by a method for manufacturing an electronic component according to an embodiment of the present invention.

  An electronic component 1 shown in FIG. 1 is disposed on a first electronic component body 2, an adhesive 3 (adhesive layer) disposed on the surface of the first electronic component body 2, and the surface of the adhesive 3. The second electronic component main body 4 is provided. The adhesive 3 is a cured adhesive and is an adhesive layer. On the first surface of the adhesive 3, the first electronic component body 2 is disposed. On the second surface opposite to the first surface side of the adhesive 3, the second electronic component body 4 is disposed. In order to form the adhesive 3, a first photocurable compound having one (meth) acryloyl group, a second photocurable compound having two or more (meth) acryloyl groups, and a photopolymerization initiator Adhesives containing are used. This adhesive is applied by an ink jet apparatus and cured to form an adhesive 3.

  Specifically, the electronic component main body includes a circuit board, a semiconductor element (including a semiconductor wafer after dicing), a semiconductor wafer, a cover glass, a capacitor, a diode, a printed board, a flexible printed board, a glass epoxy board, and a glass board. Etc. The electronic component main body may be a support member for mounting a semiconductor element.

  Since it is particularly required to form the cured adhesive with high accuracy, the first electronic component body is a semiconductor element or a support member for mounting a semiconductor element, and the second electronic component body is It is preferable that the first electronic component main body is a semiconductor wafer, and the second electronic component main body is a cover glass. It is preferable that the first electronic component body is a semiconductor element or a support member for mounting a semiconductor element, and the second electronic component body is a semiconductor element. It is preferable that the first electronic component main body is a semiconductor wafer and the second electronic component main body is a cover glass.

  It is preferable that at least one of the first electronic component main body and the second electronic component main body is a semiconductor element. The electronic component preferably includes a semiconductor element, and is preferably a semiconductor device.

  Hereinafter, an example of a method for manufacturing the electronic component shown in FIG. 1 will be described with reference to FIGS.

  First, as shown in FIG. 2A, an adhesive is applied to the first electronic component main body 2 by an inkjet device 11 to form an adhesive 12 (application process). Here, an adhesive is applied to the entire surface of the first electronic component main body 2. After application, the adhesive droplets mix with each other, resulting in the adhesive 12 in the state shown in FIG.

  As shown in FIG. 3, the ink jet device 11 includes an ink tank 21, a discharge unit 22, and a circulation flow path unit 23 inside.

  The circulation channel unit 23 includes a buffer tank 23A and a pump 23B in the circulation channel unit 23. However, like the ink jet device 11X shown in FIG. 4, the circulation flow path portion 23X may not have a buffer tank and a pump in the circulation flow path portion 23X. The circulation channel section preferably has the buffer tank in the circulation channel section, and preferably has the pump. The circulation channel section may include a flow meter, a thermometer, a filter, a liquid level sensor, and the like in addition to the buffer tank and the pump in the circulation channel section.

  The ink tank 21 stores the adhesive. The adhesive is discharged from the discharge unit 22 (inkjet head). The discharge unit 22 includes a discharge nozzle. A discharge unit 22 is connected to the ink tank 21. The ink tank 21 and the ejection part 22 are connected via a flow path. One end of the circulation flow path portion 23 is connected to the ejection portion 22, and the other end is connected to the ink tank 21. The adhesive flows inside the circulation channel portion 23.

  When the buffer tank 23A or the pump 23B is provided, the buffer tank 23A and the pump 23B are preferably disposed between the ejection unit 22 and the ink tank 21, respectively. The buffer tank 23A is disposed closer to the discharge unit 22 than the pump 23B. The pump 23B is disposed closer to the ink tank 21 than the buffer tank 23A. The adhesive is temporarily stored in the buffer tank 23A.

  Examples of the ejection unit include a thermal type, bubble jet type, electromagnetic valve type, or piezoelectric type inkjet head. Further, examples of the circulation flow path section in the discharge section include an end shooter type branching from a common circulation flow path (manifold) to the discharge nozzle and a side shooter type in which ink circulates through the discharge nozzle. From the viewpoint of further improving the formation accuracy of the finely cured adhesive by increasing the dischargeability of the adhesive, the ink jet device is an ink jet device using a piezo type ink jet head. It is preferable to apply the adhesive by action.

  With respect to the method of circulating the adhesive, it is possible to circulate by using the weight of the ink or by applying pressure, depressurization or the like using a pump or the like. A plurality of these may be used in combination. Examples of the pump include a cylinder-type non-pulsation pump, a propeller pump, a gear pump, and a diaphragm pump. From the viewpoint of increasing the circulation efficiency and further improving the formation accuracy of the fine cured adhesive, the circulation channel part preferably includes a pump for transferring the adhesive into the circulation channel part.

  In the discharge nozzle of the discharge unit, it is preferable that the pressure is maintained at an appropriate pressure and the pressure fluctuation (pulsation) is small within the range. When a pump or the like is used, it is preferable to provide an attenuator between the pump and the discharge portion in order to suppress pump pulsation. Examples of such an attenuator include a buffer tank in which the adhesive is temporarily stored and a membrane damper.

  From the viewpoint of forming the cured adhesive with higher accuracy, it is preferable that the circulation flow path portion includes a buffer tank in which the adhesive is temporarily stored in the circulation flow path portion.

  When circulating the adhesive while heating, the temperature of the adhesive can be adjusted by introducing a heater in the ink tank or using a heater in the circulation channel. Is possible.

  When the adhesive is circulated while being heated, the temperature of the adhesive is adjusted by introducing a heater in the ink tank 21 or using a heater in the circulation flow path portions 23 and 23X. It is possible.

  In the application step, after the adhesive is moved from the ink tank 21 to the discharge unit 22 in the ink jet apparatus 11, the adhesive that has not been discharged from the discharge unit 22 is allowed to flow through the circulation channel 23. The ink tank 21 is moved. Accordingly, it is preferable to apply the adhesive while circulating the adhesive in the application step.

Next, as shown in FIGS. 2B and 2C, light is irradiated from the first light irradiation unit 13 to the adhesive 12 after the coating process (first light irradiation process). Curing of the adhesive 12 is advanced by light irradiation. Thereby, the adhesive 12 </ b> A irradiated with light by the first light irradiation unit 13 is formed. In this embodiment, light is irradiated with a considerably high light illuminance. That is, the adhesive is irradiated with light so that the illuminance of light is 300 mW / cm ² or more. The adhesive 12A is a precured product and is a B-staged adhesive. It is preferable that the elastic modulus at 25 ° C. of the B-staged adhesive is 1.0 × 10 ² Pa or more and 8.0 × 10 ⁴ Pa or less.

  When light is irradiated from the second light irradiation unit 14 to be described later, the wavelength or irradiation intensity of light irradiated from the first light irradiation unit 13 and the light irradiated from the second light irradiation unit 14 to be described later The wavelength and irradiation intensity may be the same or different. When using a photocurable compound and light and a thermosetting compound, in order to control photocurability, it is preferable to perform the said 1st light irradiation process and the 2nd light irradiation process mentioned later. .

  Note that “irradiating the adhesive 12 with light from the first light irradiation unit 13” includes causing the reaction to proceed to a thickened state.

  The device that performs light irradiation is not particularly limited, and examples thereof include a light emitting diode (UV-LED) that generates ultraviolet rays, a metal halide lamp, a high pressure mercury lamp, and an ultrahigh pressure mercury lamp. From the viewpoint of further improving the formation accuracy of the cured adhesive, it is particularly preferable to use a UV-LED for the first light irradiation section.

Next, as shown in FIGS. 2C and 2D, after the first light irradiation step, the second light irradiation unit 14, which is different from the first light irradiation unit 13, The adhesive 12A irradiated with light from the light irradiation unit 13 may be irradiated with light (second light irradiation step). It may be possible to further advance the curing of the adhesive 12A by light irradiation. Thereby, the adhesive 12 </ b> B irradiated with light by the second light irradiation unit 14 is formed. The adhesive 12B is a pre-cured product and is a B-staged adhesive. The elastic modulus at 25 ° C. of the surface of the B-staged adhesive is preferably 1.0 × 10 ² Pa or more and 8.0 × 10 ⁴ Pa or less. Of the B-staged adhesive after the second light irradiation step and the B-staged adhesive after the first light irradiation, the surface of the B-staged adhesive after the first light irradiation. The elastic modulus at 25 ° C. is preferably 5.0 × 10 ² Pa or more and 8.0 × 10 ⁴ Pa or less. The elastic modulus at 25 ° C. of both surfaces of the B-staged adhesive after the second light irradiation step and the B-staged adhesive after the first light irradiation is 5.0 × 10 ² Pa or more. 8.0 × 10 ⁴ Pa or less is more preferable.

  The elastic modulus is measured at 25 ° C. using a viscoelasticity measuring device ARES manufactured by TA Instruments Inc., a measurement plate: a parallel plate having a diameter of 8 mm, and a frequency of 1 Hz. In the present specification, the elastic modulus means storage elastic modulus (G ′).

  Said 2nd light irradiation process is preferably performed before the arrangement | positioning process mentioned later, and it is preferable to be performed before a heating process. From the viewpoint of forming the cured adhesive with higher accuracy, the second light irradiation step is preferably performed. However, the second light irradiation step is not necessarily performed, and an arrangement step described later may be performed after the first light irradiation step without performing the second light irradiation step.

  Next, as shown in FIGS. 2D and 2E, after the second light irradiation step, the second electronic component main body 4 is disposed on the adhesive 12B irradiated with light (arrangement). Process / stacking process). The first electronic component main body 2 and the second electronic component main body 4 are bonded to each other by applying pressure through the adhesive 12B irradiated with light to obtain the primary laminate 1A. If the second light irradiation step is not performed after the first light irradiation step, the second electronic component main body 4 is disposed on the adhesive 12A irradiated with light. In this case, the first electronic component main body 2 and the second electronic component main body 4 are bonded together by applying pressure through the adhesive 12 </ b> A irradiated with light to obtain a primary laminate.

  Next, the adhesive is heated after the placement step (heating step). The primary laminate 1A is heated to cure the adhesive 12B between the first electronic component main body 2 and the second electronic component main body 4 to obtain an electronic component. In this way, the electronic component 1 shown in FIG. 1 can be obtained.

  The adhesive may be multilayered by repeating the coating step and the first light irradiation step to form a multilayer adhesive. As shown in FIG. 5, you may obtain the electronic component 31 provided with the adhesive agent 32 by which several adhesive agent 32A, 32B, 32C was laminated | stacked.

  In the method for manufacturing an electronic component, the temperature of the circulating adhesive is preferably 30 from the viewpoint of improving the dischargeability and transportability of the adhesive and forming the cured adhesive with higher accuracy. ℃ or higher, more preferably 40 ℃ or higher, preferably 120 ℃ or lower, more preferably 100 ℃ or lower.

  From the viewpoint of forming the cured adhesive with higher accuracy, the pressure applied at the time of bonding in the arrangement step is preferably 0.01 MPa or more, more preferably 0.05 MPa or more, preferably 10 MPa or less, more preferably Is 8 MPa or less.

  From the viewpoint of forming the cured adhesive with higher accuracy, in the arrangement step, the temperature at the time of bonding is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, preferably 150 ° C. or lower, more preferably 130. It is below ℃.

  The adhesive includes a first photocurable compound having one (meth) acryloyl group (a curable compound curable by light irradiation) and a second photocuring having two or more (meth) acryloyl groups. A curable compound (a curable compound that can be cured by light irradiation) and a photopolymerization initiator. The adhesive preferably includes a thermosetting compound (a curable compound that can be cured by heating) and a thermosetting agent. The adhesive preferably contains light and a thermosetting compound (a curable compound that can be cured by both light irradiation and heating) and a thermosetting agent. The adhesive preferably contains a curing accelerator.

  Hereinafter, the detail of each component which can be used for the said adhesive agent is demonstrated.

(Photocurable compound)
Examples of the photocurable compound include a curable compound having a (meth) acryloyl group, a curable compound having a vinyl group, and a curable compound having a maleimide group. From the viewpoint of curing well with high light illuminance, suppressing the generation of outgas, and effectively increasing the adhesive strength, the adhesive is composed of the first photocurable compound (first photocurable compound (A1)). And the second curable compound (referred to as the first photocurable compound (A2)). From the viewpoint of forming a cured adhesive with high accuracy, the photocurable compound includes a first photocurable compound having a (meth) acryloyl group (one or more). In addition, the combined use of the first photocurable compound and the second photocurable compound further suppresses voids, and can further improve the adhesiveness, moisture-resistant adhesion reliability and cooling cycle reliability, and is cured. The adhesive can be formed with high accuracy. As for a 1st photocurable compound (A1) and a 2nd photocurable compound (A2), only 1 type may respectively be used and 2 or more types may be used together.

  In the present specification, the curable compound having a (meth) acryloyl group means a compound having at least one of a methacryloyl group and an acryloyl group.

  The first photocurable compound (A1) is, for example, a monofunctional compound. The second photocurable compound (A2) is, for example, a polyfunctional compound. Since the second photocurable compound (A2) has two or more (meth) acryloyl groups, polymerization proceeds and cures upon irradiation with light.

  As the second photocurable compound (A2), (meth) acrylic acid adduct of polyhydric alcohol, (meth) acrylic acid adduct of alkylene oxide modified product of polyhydric alcohol, urethane (meth) acrylates, and Examples include polyester (meth) acrylates. Examples of the polyhydric alcohol include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylol propane, cyclohexane dimethanol, tricyclodecane dimethanol, an alkylene oxide adduct of bisphenol A, and Examples include pentaerythritol.

  The second photocurable compound (A2) may be a bifunctional (meth) acrylate, a trifunctional methacrylate, or a tetrafunctional or higher (meth) acrylate.

  Examples of the bifunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanedi (meth) acrylate, and 1,10- Decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) acrylate, ethoxylated cyclohexanemethanol di ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butylbutanediol di (meth) acrylate, 2-ethyl-2- Butylp Panjioruji (meth) acrylate, tricyclodecane di (meth) acrylate, and dipropylene glycol di (meth) acrylate.

  Examples of trifunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, propionate dipentaerythritol tri (meth) acrylate, tri ((meta And acryloyloxyethyl) isocyanurate and sorbitol tri (meth) acrylate.

  Examples of the tetrafunctional (meth) acrylate include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate propionate. It is done.

  Examples of pentafunctional (meth) acrylates include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Examples of the hexafunctional (meth) acrylate include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, and phosphazene alkylene oxide-modified hexa (meth) acrylate.

  The term “(meth) acrylate” refers to acrylate or methacrylate. The term “(meth) acryl” refers to acryl or methacryl.

  The second photocurable compound (A2) is preferably a second photocurable compound having a polycyclic skeleton or a urethane skeleton and having two or more (meth) acryloyl groups. By using this second photocurable compound, the moisture and heat resistance of the cured adhesive can be increased. Therefore, the reliability of the electronic component can be increased. The second photocurable compound (A2) may have a polycyclic skeleton or a urethane skeleton.

  Specific examples of the second photocurable compound having a polycyclic skeleton and having two or more (meth) acryloyl groups include tricyclodecane dimethanol di (meth) acrylate, isobornyl dimethanol di (meta) ) Acrylate and dicyclopentenyl dimethanol di (meth) acrylate. From the viewpoint of further improving the moisture resistance and heat-and-moisture resistance of the cured adhesive, the second photocurable compound (A2) is preferably tricyclodecane dimethanol di (meth) acrylate.

  The polycyclic skeleton indicates a structure having a plurality of cyclic skeletons continuously. Specifically, the polycyclic skeleton is a skeleton in which two or more rings are integrated in a form sharing two or more atoms, and has a condensed ring. The polycyclic skeleton is not a skeleton in which an alkylene group is present between two rings, for example. Examples of the polycyclic skeleton include a polycyclic alicyclic skeleton and a polycyclic aromatic skeleton.

  Examples of the polycyclic alicyclic skeleton include a bicycloalkane skeleton, a tricycloalkane skeleton, a tetracycloalkane skeleton, and an isobornyl skeleton.

  Examples of the polycyclic aromatic skeleton include naphthalene ring skeleton, anthracene ring skeleton, phenanthrene ring skeleton, tetracene ring skeleton, chrysene ring skeleton, triphenylene ring skeleton, tetraphen ring skeleton, pyrene ring skeleton, pentacene ring skeleton, picene ring skeleton and Examples include perylene ring skeletons.

  From the viewpoint of further improving insulation reliability and adhesion reliability, the photocurable compound preferably contains a photocurable compound having a dicyclopentadiene skeleton.

  The polyfunctional compound having a urethane skeleton and having two or more (meth) acryloyl groups is not particularly limited, and can be obtained, for example, by the following method. A polyol and a bifunctional or higher functional isocyanate are reacted, and the remaining isocyanate group is further reacted with a (meth) acryl monomer having an alcohol or an acid group. You may make the (meth) acryl monomer which has a hydroxyl group react with bifunctional or more isocyanate. Specifically, for example, 1 mol of trimethylolpropane and 3 mol of isophorone diisocyanate are reacted under a tin-based catalyst. The urethane-modified (meth) acrylic compound is obtained by reacting the isocyanate group remaining in the obtained compound with hydroxyethyl acrylate, which is an acrylic monomer having a 2-mol hydroxyl group.

  The polyol is not particularly limited, and examples thereof include ethylene glycol, glycerin, sorbitol, trimethylolpropane, and (poly) propylene glycol.

  The isocyanate is not particularly limited as long as it is bifunctional or higher. Examples of the isocyanate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), and hydrogenated MDI. , Polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylene Examples include diisocyanate and 1,6,10-undecane triisocyanate.

  Specific examples of the first photocurable compound (A1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl (meth). Acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) ) Acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl ( Meta Acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene Glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2-ethylhexyl (meth) acrylate, Dihydroxycyclopentadienyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, di Kuropentaniru (meth) acrylate, naphthyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.

  From the viewpoint of further suppressing voids and further improving adhesion, moisture-resistant adhesion reliability, and cooling cycle reliability, the first photocurable compound (A1) may contain 2-ethylhexyl (meth) acrylate. preferable.

  Examples of the photocurable compound having a vinyl group include vinyl ethers, ethylene derivatives, styrene, chloromethyl styrene, α-methyl styrene, maleic anhydride, dicyclopentadiene, N-vinyl pyrrolidone, and N-vinyl formamide.

  The photocurable compound having a maleimide group is not particularly limited. For example, N-methylmaleimide, N-ethylmaleimide, N-hexylmaleimide, N-propylmaleimide, N-butylmaleimide, N-octylmaleimide, N- Dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, Np-carboxyphenylmaleimide, Np-hydroxyphenylmaleimide, Np-chlorophenylmaleimide, Np-tolylmaleimide, Np-xylylmaleimide N-o-chlorophenylmaleimide, N-o-tolylmaleimide, N-benzylmaleimide, N-2,5-diethylphenylmaleimide, N-2,5-dimethylphenylmaleimide, Nm-tolylmaleimide, N-α -Naphthylmaleimide N-o-xylylmaleimide, Nm-xylylmaleimide, bismaleimide methane, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, bismaleimide dodecane, N, N′-m-phenylene dimaleimide N, N′-p-phenylenedimaleimide, 4,4′-bismaleimide diphenyl ether, 4,4′-bismaleimide diphenylmethane, 4,4′-bismaleimide-di (3-methylphenyl) methane, 4,4 '-Bismaleimide-di (3-ethylphenyl) methane, 4,4'-Bismaleimide-di (3-methyl-5-ethyl-phenyl) methane, N, N'-(2,2-bis- (4 -Phenoxyphenyl) propane) dimaleimide, N, N'-2,4-tolylenedialeimide, N, N'-2,6-tolylenedialeimi And N, N′-m-xylylene dimaleimide and the like.

  From the viewpoint of forming the cured adhesive with higher accuracy, the total content of the first photocurable compound (A1) and the second photocurable compound (A2) in 100% by weight of the adhesive. The amount is preferably 5% by weight or more, more preferably 10% by weight or more, preferably 80% by weight or less, more preferably 70% by weight or less. From the viewpoint of further increasing the thickness accuracy of the cured adhesive and further reducing the occurrence of voids in the cured adhesive, the first photocurable compound (A1) and the second of 100% by weight of the adhesive are used. The total content of the photocurable compound (A2) is particularly preferably 5% by weight or more and 80% by weight or less.

  From the viewpoint of suppressing generation of outgas, further suppressing voids, and further improving adhesiveness, moisture-resistant adhesion reliability and thermal cycle reliability, when the adhesive does not contain light and thermosetting compounds described later, In the case where the adhesive contains light and a thermosetting compound described later in a total of 100% by weight of the first photocurable compound (A1) and the second photocurable compound (A2), the first light The content of the first photocurable compound (A1) is 50% by weight in a total of 100% by weight of the curable compound (A1), the second photocurable compound (A2), and the light and thermosetting compound. As mentioned above, it is preferable that 99.95 weight% or less and content of the 2nd photocurable compound (A2) are 0.05 weight% or more and 50 weight% or less, and the 1st photocurable compound (A1). Content of 70 wt% or more and 99.9 wt% or less, the second light The content of the curable compound (A2) is more preferably 0.1 wt% or more and 30 wt% or less, and the content of the first photocurable compound (A1) is 80 wt% or more, 99.5 More preferably, the content of the second photocurable compound (A2) is 0.5% by weight or more and 20% by weight or less. When the content ratio between the first photocurable compound (A1) and the second photocurable compound (A2) satisfies the above relationship, the cured adhesive is irradiated even when irradiated with light with high light illuminance. Outgassing is less likely to occur.

  From the viewpoint of further suppressing voids and further improving the adhesion, moisture-resistant adhesion reliability and cooling cycle reliability, the content of the first photocurable compound (A1) in 100% by weight of the adhesive, and 2 -Ethylhexyl (meth) acrylate content is preferably 0.05% by weight or more, more preferably 0.1% by weight or more, preferably 70% by weight or less, more preferably 50% by weight or less.

(Light and thermosetting compounds)
From the viewpoint of further improving the thickness accuracy of the cured adhesive, making it harder to generate voids in the cured adhesive, and improving the reliability of the cooling and heating cycle, etc., the adhesive is composed of light and a thermosetting compound. It is preferable to contain. Examples of the light and thermosetting compounds include compounds having various photocurable functional groups and various thermosetting functional groups. From the viewpoint of forming the cured adhesive with higher accuracy, the light and thermosetting compound preferably has one or more (meth) acryloyl groups and one or more cyclic ether groups. It is preferable to have at least one (meth) acryloyl group and at least one epoxy group. As for the said light and a thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  The photocurable compound, the first photocurable compound, the second photocurable compound, and the thermosetting compound are preferably blended as components different from the light and thermosetting compound. .

  Although it does not specifically limit as said light and a thermosetting compound, The compound which has a (meth) acryloyl group and an epoxy group, the partial (meth) acrylate of an epoxy compound, a urethane modified (meth) acryl epoxy compound, etc. are mentioned.

  Examples of the compound having the (meth) acryloyl group and the epoxy group include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether.

  The partial (meth) acrylated product of the epoxy compound can be obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a catalyst according to a conventional method. Examples of the epoxy compound that can be used for the partial (meth) acrylate of the epoxy compound include novolac-type epoxy compounds and bisphenol-type epoxy compounds. Examples of the novolak type epoxy compound include a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, a biphenyl novolak type epoxy compound, a trisphenol novolak type epoxy compound, a dicyclopentadiene novolak type epoxy compound, and the like. Examples of the bisphenol type epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a 2,2′-diallyl bisphenol A type epoxy compound, a hydrogenated bisphenol type epoxy compound, and a polyoxypropylene bisphenol A type epoxy compound. Can be mentioned. By appropriately changing the blending amount of the epoxy compound and (meth) acrylic acid, an epoxy compound having a desired acrylate ratio can be obtained. The blending amount of the carboxylic acid with respect to 1 equivalent of epoxy group is preferably 0.1 equivalent or more, more preferably 0.2 equivalent or more, preferably 0.7 equivalent or less, more preferably 0.5 equivalent or less.

  The urethane-modified (meth) acryl epoxy compound is obtained, for example, by the following method. A polyol and a bifunctional or higher functional isocyanate are reacted, and the remaining isocyanate group is reacted with a (meth) acryl monomer having an acid group and glycidol. Alternatively, a (meth) acryl monomer having a hydroxyl group in a bifunctional or higher isocyanate and glycidol may be reacted without using a polyol. Alternatively, the urethane-modified (meth) acryl epoxy compound can be obtained by reacting glycidol with a (meth) acrylate monomer having an isocyanate group. Specifically, for example, first, 1 mol of trimethylolpropane and 3 mol of isophorone diisocyanate are reacted under a tin-based catalyst. The urethane-modified (meth) acrylic epoxy compound is obtained by reacting the isocyanate group remaining in the obtained compound with hydroxyethyl acrylate which is an acrylic monomer having a hydroxyl group and glycidol which is an epoxy having a hydroxyl group.

  The polyol is not particularly limited, and examples thereof include ethylene glycol, glycerin, sorbitol, trimethylolpropane, and (poly) propylene glycol.

  The isocyanate is not particularly limited as long as it is bifunctional or higher. Examples of the isocyanate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), and hydrogenated MDI. , Polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylene Examples include diisocyanate and 1,6,10-undecane triisocyanate.

  From the viewpoint of further increasing the thickness accuracy of the cured adhesive and further reducing the occurrence of voids in the cured adhesive, the light and thermosetting compound preferably contains 4-hydroxybutyl acrylate glycidyl ether. .

  From the viewpoint of forming the cured adhesive with higher accuracy, the content of the light and thermosetting compound in the adhesive of 100% by weight is preferably 0.5% by weight or more, more preferably 1% by weight. % Or more, preferably 80% by weight or less, more preferably 70% by weight or less.

  From the viewpoint of forming the cured adhesive with higher accuracy, the total content of the photocurable compound and the light and thermosetting compound is preferably 10% by weight in 100% by weight of the adhesive. Above, more preferably 20% by weight or more, preferably 80% by weight or less, more preferably 70% by weight or less.

(Thermosetting compound)
Examples of the thermosetting compound include a thermosetting compound having a cyclic ether group and a thermosetting compound having a thiirane group. From the viewpoint of forming the cured adhesive with higher accuracy, a thermosetting compound having one or more cyclic ether groups is used as the thermosetting compound. The thermosetting compound having a cyclic ether group is more preferably a thermosetting compound having an epoxy group (epoxy compound). As for the said thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  The epoxy compound is not particularly limited, and examples thereof include novolak type epoxy compounds and bisphenol type epoxy compounds. Examples of the novolak type epoxy compound include a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, a biphenyl novolak type epoxy compound, a trisphenol novolak type epoxy compound, a dicyclopentadiene novolak type epoxy compound, and the like. Examples of the bisphenol type epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a 2,2′-diallyl bisphenol A type epoxy compound, a hydrogenated bisphenol type epoxy compound, and a polyoxypropylene bisphenol A type epoxy compound. Can be mentioned. In addition, examples of the epoxy compound include a cycloaliphatic epoxy compound and glycidylamine.

  From the viewpoint of forming a cured adhesive with higher accuracy and making it more difficult for voids to occur in the cured adhesive, the thermosetting compound preferably has an aromatic skeleton.

  From the viewpoint of further suppressing voids and further improving the adhesiveness, moisture-resistant adhesion reliability, and cooling cycle reliability, the thermosetting compound having one or more cyclic ether groups is preferably solid at 25 ° C. From the viewpoint of further suppressing voids and further improving adhesion, moisture-resistant adhesion reliability, and cooling cycle reliability, the softening point of the thermosetting compound having one or more cyclic ether groups is preferably 25 ° C or higher. More preferably, it is 30 degreeC or more, More preferably, it is 40 degreeC or more. The upper limit of the softening point is not particularly limited. The softening point of the thermosetting compound having one or more cyclic ether groups is preferably 150 ° C. or lower.

  The softening point can be measured according to JIS K7234.

  From the viewpoint of forming the cured adhesive with higher accuracy, the content of the thermosetting compound in 100% by weight of the adhesive is preferably 10% by weight or more, more preferably 20% by weight or more, preferably Is 80% by weight or less, more preferably 70% by weight or less.

(Photopolymerization initiator)
Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. As for the said photoinitiator, only 1 type may be used and 2 or more types may be used together.

  The photo radical polymerization initiator is not particularly limited. The photo radical polymerization initiator is a compound for generating radicals upon light irradiation and initiating a radical polymerization reaction. Specific examples of the photo radical polymerization initiator include, for example, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; 2-hydroxy-2-methyl-1-phenyl-propan-1-one An acetophenone compound such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone- Aminoacetophenone compounds such as 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone; Anthraquinone compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone; thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A ketal compound such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc. Ruphosphine oxide compound; 1,2-octanedione, 1- [4- (phenylthio) -2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H Oxime ester compounds such as -carbazol-3-yl] -1- (o-acetyloxime); bis (cyclopentadienyl) -di-phenyl-titanium, bis (cyclopentadienyl) -di-chloro-titanium, Bis (cyclopentadienyl) -bis (2,3,4,5,6-pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrol-1-yl) And titanocene compounds such as phenyl) titanium. As for the said radical photopolymerization initiator, only 1 type may be used and 2 or more types may be used together.

  A photopolymerization initiation assistant may be used together with the photopolymerization initiator. Examples of the photopolymerization initiation assistant include N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. Photopolymerization initiation assistants other than these may be used. As for the said photoinitiation adjuvant, only 1 type may be used and 2 or more types may be used together.

  In 100% by weight of the adhesive, the content of the photopolymerization initiator is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less. It is.

(Thermosetting agent)
Examples of the thermosetting agent include organic acids, amine compounds, amide compounds, hydrazide compounds, imidazole compounds, imidazoline compounds, phenol compounds, urea compounds, polysulfide compounds, and acid anhydrides. A modified polyamine compound such as an amine-epoxy adduct may be used as the thermosetting agent. Thermosetting agents other than these may be used.

  The amine compound means a compound having one or more primary to tertiary amino groups. Examples of the amine compound include (1) aliphatic amine, (2) alicyclic amine, (3) aromatic amine, (4) hydrazide, and (5) guanidine derivative. Also, epoxy compound-added polyamine (reaction product of epoxy compound and polyamine), Michael addition polyamine (reaction product of α, β-unsaturated ketone and polyamine), Mannich addition polyamine (condensate of polyamine, formalin and phenol), thiourea Adducts such as addition polyamine (reaction product of thiourea and polyamine) and ketone-capped polyamine (reaction product of ketone compound and polyamine [ketimine]) may also be used.

  Examples of the (1) aliphatic amine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine.

  Examples of the (2) alicyclic amine include mensendiamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5, 5) Undecane adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane and the like.

  As the above (3) aromatic amine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl- 2,6-diaminotoluene, 2,4-diaminoanisole, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-methylene-bis [2-chloroaniline], 4,4 ′ -Diaminodiphenyl ether, 2,2-bis [4- [4-aminophenoxy] phenyl] propane, bis [4- [4-aminophenoxy] phenyl] sulfone, 1,3-bis [4-aminophenoxy] benzene, methylenebis -(2-ethyl-6methylaniline), 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 3,3 ', , 5'-tetraethyl-4,4'-diaminodiphenylmethane and the like.

  Examples of (4) hydrazide include carbodihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, and isophthalic acid dihydrazide.

  Examples of the guanidine derivative (5) include dicyandiamide, 1-o-tolyldiguanide, α-2,5-dimethylguanide, α, ω-diphenyldiguanide, α, α-bisguanylguanidinodiphenyl ether, p-chlorophenyldiguanide, Examples include α, α-hexamethylenebis [ω- (p-chlorophenol)] diguanide, phenyldiguanide oxalate, acetylguanidine, and diethylcyanoacetylguanidine.

  Examples of the phenol compound include polyhydric phenol compounds. Examples of the polyhydric phenol compound include phenol, cresol, ethylphenol, butylphenol, octylphenol, bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, 4,4′-biphenylphenol, naphthalene skeleton-containing phenol novolac resin, Examples thereof include a xylylene skeleton-containing phenol novolak resin, a dicyclopentadiene skeleton-containing phenol novolak resin, and a fluorene skeleton-containing phenol novolak resin.

  Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic acid, pyromellitic anhydride, Examples include benzophenone tetracarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, trimellitic anhydride, and polyazeline acid anhydride.

  From the viewpoint of further increasing the thickness accuracy of the cured adhesive and making it more difficult for voids to occur in the cured adhesive, the thermosetting agent preferably contains an acid anhydride or an aromatic amine. It is more preferable to contain a group amine.

  The content of the thermosetting agent in 100% by weight of the adhesive is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 60% by weight or less, more preferably 50% by weight or less.

(Curing accelerator)
Examples of the curing accelerator include tertiary amines, imidazoles, quaternary ammonium salts, quaternary phosphonium salts, organometallic salts, phosphorus compounds, urea compounds, and the like.

  In 100% by weight of the adhesive, the content of the curing accelerator is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less. is there.

(solvent)
The adhesive does not contain or contains a solvent. The said adhesive agent may contain the solvent and does not need to contain it. From the viewpoint of further increasing the thickness accuracy of the cured adhesive and further making it difficult for voids to occur in the cured adhesive, the smaller the solvent content in the adhesive, the better.

  Examples of the solvent include water and organic solvents. From the viewpoint of further improving the removability of the residue, an organic solvent is preferable. Examples of the organic solvent include alcohols such as ethanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, and methylcarbitol. , Butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, glycol ethers such as tripropylene glycol monomethyl ether, ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene Recall monomethyl ether acetate, esters such as propylene carbonate, octane, aliphatic hydrocarbons decane, and petroleum ether, petroleum solvents such as naphtha.

  When the adhesive contains the solvent, the content of the solvent in 100% by weight of the adhesive is preferably 5% by weight or less, more preferably 1% by weight or less, and further preferably 0.5% by weight or less. It is.

(Filler)
The adhesive does not contain or contains a filler. The adhesive may or may not contain a filler. From the viewpoint of further increasing the thickness accuracy of the cured adhesive and further making it difficult for voids to occur in the cured adhesive, the smaller the filler content in the adhesive, the better. Furthermore, the smaller the filler content in the adhesive, the lower the occurrence of ejection failure by the ink jet apparatus.

  Examples of the filler include silica, talc, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, aluminum nitride, and boron nitride.

  When the adhesive contains the filler, the content of the filler in 100% by weight of the adhesive is preferably 5% by weight or less, more preferably 1% by weight or less, and further preferably 0.5% by weight or less. It is.

(Other ingredients)
The adhesive may contain other components. Although it does not specifically limit as another component, Adhesion adjuvants, such as a coupling agent, a pigment, dye, a leveling agent, an antifoamer, a polymerization inhibitor, etc. are mentioned.

(Specific examples of electronic components)
Hereinafter, other specific examples of the electronic component will be described.

  FIG. 6 is a front sectional view schematically showing a first modification of the electronic component.

  A semiconductor device 71 shown in FIG. 6 is an electronic component. The semiconductor device 71 includes a substrate 53 </ b> A, an adhesive 72, and a first semiconductor wafer 73. The substrate 53A has a first connection terminal 53a on the upper surface. The first semiconductor wafer 73 has connection terminals 73a on the upper surface. The substrate 53A is formed in the same manner as the substrate 53 described later except that the second connection terminal 53b is not provided.

  A first semiconductor wafer 73 is laminated on the substrate 53A via an adhesive 72. The adhesive 72 is formed by photocuring the adhesive.

  The first semiconductor wafer 73 has connection terminals 73a on the upper surface. A wiring 74 is drawn from the connection terminal 73a. By the wiring 74, the connection terminal 73a and the first connection terminal 53a are electrically connected.

  FIG. 7 is a front sectional view schematically showing a second modification of the electronic component.

  A semiconductor device 51 shown in FIG. 7 is an electronic component. The semiconductor device 51 includes a laminated structure 52. The laminated structure 52 includes a substrate 53, an adhesive 54, and a second semiconductor wafer 55 laminated on the substrate 53 via the adhesive 54. A second semiconductor wafer 55 is disposed on the substrate 53. On the substrate 53, the second semiconductor wafer 55 is indirectly laminated. The substrate 53 is larger than the second semiconductor wafer 55 in plan view. The substrate 53 has a region projecting laterally from the second semiconductor wafer 55.

  The adhesive 54 is formed, for example, by curing the adhesive. The adhesive before curing may have tackiness. In order to form an adhesive before curing, an adhesive sheet may be used.

  The substrate 53 has a first connection terminal 53a on the upper surface. The second semiconductor wafer 55 has connection terminals 55a on the upper surface. A wiring 56 is drawn from the connection terminal 55a. One end of the wiring 56 is connected to a connection terminal 55 a provided on the second semiconductor wafer 55. The other end of the wiring 56 is connected to a first connection terminal 53 a provided on the substrate 53. By the wiring 56, the connection terminal 55a and the first connection terminal 53a are electrically connected. The other end of the wiring 56 may be connected to a connection terminal other than the first connection terminal 53a. The wiring 56 is preferably a bonding wire.

  A first semiconductor wafer 62 is laminated on the second semiconductor wafer 55 in the laminated structure 52 via an adhesive 61. The adhesive 61 is formed by photocuring the adhesive.

  The substrate 53 has a second connection terminal 53b on the upper surface. The first semiconductor wafer 62 has connection terminals 62a on the upper surface. A wiring 63 is drawn from the connection terminal 62a. One end of the wiring 63 is connected to a connection terminal 62 a provided on the first semiconductor wafer 62. The other end of the wiring 63 is connected to a second connection terminal 53 b provided on the substrate 53. The connection terminal 62 a and the second connection terminal 53 b are electrically connected by the wiring 63. The other end of the wiring 63 may be connected to a connection terminal other than the second connection terminal 53b. The wiring 63 is preferably a bonding wire.

  The semiconductor device 51 can be obtained by forming an adhesive 61 on the second semiconductor wafer 55 by discharging a liquid adhesive having photocurability and thermosetting property from the ink jet apparatus. it can. On the other hand, the semiconductor device 71 is obtained by ejecting a liquid adhesive having photocurability and thermosetting properties from the ink jet device to form the adhesive 72 on the substrate 53A. Can do.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.

(Preparation of adhesives A to C)
The components shown in Tables 1 and 2 below were blended in the blending amounts shown in Table 2 below and mixed uniformly to obtain adhesives A to C.

(Examples 1, 5, and 8)
2A to 2C according to the method for manufacturing an electronic component according to the embodiment of the present invention described above on a silicon wafer using the adhesives shown in Table 2 among the obtained adhesives A to C. An adhesive layer was formed through each step shown in FIG. That is, using the ink jet apparatus, the adhesive was applied on a silicon wafer while being circulated at 70 ° C. (application process). Next, the adhesive is irradiated with light (first light irradiation step; using a UV-LED lamp having a main wavelength of 365 nm, light irradiation with an illuminance of 300 mW / cm ² is repeated 8 times to obtain a total integrated light amount. Was set to 600 mJ / cm ² ), thereby forming an adhesive layer having a thickness of 30 μm to obtain a measurement sample.

(Example 2)
Using the obtained adhesive A, an adhesive layer is obtained through the steps shown in FIGS. 2A to 2D according to the method for manufacturing an electronic component according to the embodiment of the present invention described above on a silicon wafer. Formed. That is, using the ink jet apparatus, the adhesive was applied on a silicon wafer while being circulated at 70 ° C. (application process). Next, the adhesive is irradiated with light (first light irradiation step; using a UV-LED lamp having a main wavelength of 365 nm, light irradiation with an illuminance of 300 mW / cm ² is repeated 8 times to obtain a total integrated light amount. Was 600 mJ / cm ^2. ). Further, the adhesive was irradiated with light (second light irradiation step; using an ultra-high pressure mercury lamp, irradiated at an illuminance of 100 mW / cm ² for 10 seconds, so that the total accumulated light amount was 1000 mJ / cm ² . Then, an adhesive layer having a thickness of 30 μm was formed as a measurement sample.

(Examples 3, 6, and 9)
Using the adhesives shown in Table 2 among the obtained adhesives A to C, except that in the first light irradiation step, the illuminance was 1000 mW / cm ² and the total integrated light amount was 2000 mJ / cm ^2. A measurement sample was prepared in the same manner as in Example 1.

(Examples 4, 7, and 10)
Using the adhesives shown in Table 2 among the obtained adhesives A to C, in the first light irradiation step, the illuminance was 2000 mW / cm ² and the total integrated light amount was 4000 mJ / cm ^2. A measurement sample was prepared in the same manner as in Example 1.

(Comparative Example 1)
A measurement sample was prepared in the same manner as in Example 1 except that in the first light irradiation step, the illuminance was 200 mW / cm ² and the total integrated light amount was 400 mJ / cm ² .

(Comparative Examples 2-7)
For Comparative Examples 2, 4 and 6, using the adhesives shown in Table 2 among the obtained adhesives A to C, the illuminance was set to 200 mW / cm ² in the first light irradiation step, and the total integrated light amount A measurement sample was prepared in the same manner as in Example 2 except that was set to 400 mJ / cm ² .

For Comparative Examples 3, 5 and 7, using the adhesives shown in Table 2 among the obtained adhesives A to C, the illuminance was set to 100 mW / cm ² in the first light irradiation step, and the total integrated light amount A measurement sample was prepared in the same manner as in Example 2 except that was set to 200 mJ / cm ² .

(Evaluation)
(Outgas amount)
After measuring the weight of the measurement sample obtained above, it was put in an oven at 160 ° C. and heated for 3 hours, and then the weight was measured again to calculate the outgas amount.

[Outgas amount judgment criteria]
○○: Outgas amount is less than 0.1% ○: Outgas amount is 0.1% or more and less than 0.15% Δ: Outgas amount is 0.15% or more and less than 0.3% ×: Outgas amount is 0. 3% or more

(Photoreaction rate)
The obtained measurement sample was measured using an infrared spectroscopic hardness meter (7000 eFT-IR / 600UMA, manufactured by Varian). Separate the peak area of the (meth) acryloyl groups after curing and peak area (820～800Cm ^-1) of (meth) acryloyl groups before curing was measured (820～800Cm ^-1) and the reference peak area (780～720Cm ^{- The} reaction rate was calculated by comparing as ¹ ). The reaction rate of the (meth) acryloyl group was calculated from the following formula.

  Reaction rate of (meth) acryloyl group = {peak area of (meth) acryloyl group before curing−peak area of (meth) acryloyl group after curing × reference peak area before curing / reference peak area after curing} / curing Peak area of previous (meth) acryloyl group × 100

(Adhesive strength after heat test)
On the obtained measurement sample, using a die-bonding apparatus, a silicon bare chip as a semiconductor chip (length 3 mm × width 3 mm × thickness 750 μm) was pressurized at 110 ° C. for 0.1 second under a condition of 0.1 MPa, and a 160 ° C. oven. The adhesive test piece was obtained by carrying out thermosetting by putting in and heating for 3 hours. After measuring the die shear strength using a die shear strength measuring device (“Dage series 4000” manufactured by Dage, test temperature: 260 ° C.), and placing an unmeasured adhesive test piece in an oven at 260 ° C., heating for 1 hour The die shear strength after the heat-resistant adhesion test was measured using a die shear strength measuring device (“Dage series 4000” manufactured by Dage, test temperature: 260 ° C.). The heat-resistant adhesion reliability test was judged according to the following criteria.

[Criteria for heat-resistant adhesion reliability test]
○: Decrease in adhesive strength is 0% or more and less than 10% ○: Decrease in adhesive strength is 10% or more and less than 50% Δ: Decrease in adhesive strength is 50% or more and less than 70% ×: Decrease in adhesive strength 70% or more

  Details of the blending components used are shown in Table 1 below, and the composition and results are shown in Table 2 below. The blending unit of the blending component is parts by weight.

DESCRIPTION OF SYMBOLS 1 ... Electronic component 1A ... Primary laminated body 2 ... 1st electronic component main body 3 ... Adhesive (after heating)
DESCRIPTION OF SYMBOLS 4 ... 2nd electronic component main body 11, 11X ... Inkjet apparatus 12 ... Adhesive 12A ... Adhesive irradiated with light by 1st light irradiation part 12B ... Adhesive irradiated with light by 2nd light irradiation part DESCRIPTION OF SYMBOLS 13 ... 1st light irradiation part 14 ... 2nd light irradiation part 21 ... Ink tank 22 ... Ejection part 23,23X ... Circulation flow path part 23A ... Buffer tank 23B ... Pump 31 ... Electronic component 32 ... Multi-layer adhesive ( After heating)
32A, 32B, 32C ... Adhesive (after heating)
DESCRIPTION OF SYMBOLS 51,71 ... Semiconductor device 52 ... Laminated structure 53, 53A ... Board | substrate 53a ... 1st connection terminal 53b ... 2nd connection terminal 54, 61, 72 ... Adhesive 55 ... 2nd semiconductor wafer 55a, 73a ... Connection Terminals 56, 63, 74 ... Wiring 62, 73 ... First semiconductor wafer 62a ... Connection terminal

Claims (9)

An application step of applying an adhesive having photocurability on the surface of the first electronic component body using an inkjet device;
A light irradiation step of irradiating the adhesive with light so that the illuminance of light is 300 mW / cm ² or more;
A disposing step of disposing a second electronic component main body on a surface opposite to the first electronic component main body side of the adhesive;
The adhesive includes a first photocurable compound having one (meth) acryloyl group, a second photocurable compound having two or more (meth) acryloyl groups, and a photopolymerization initiator. Manufacturing method of electronic components. The adhesive has photocurability and thermosetting;
The adhesive includes a thermosetting compound and a thermosetting agent,
The manufacturing method of the electronic component of Claim 1 provided with the heating process which heats the said adhesive agent. Does not contain or contain light and thermosetting compounds,
In the case where the adhesive does not contain the light and thermosetting compound, the first photocurable is included in 100% by weight of the total of the first photocurable compound and the second photocurable compound. The content of the compound is 70% by weight or more and 99.9% by weight or less, and the content of the second photocurable compound is 0.1% by weight or more and 30% by weight or less,
When the adhesive contains the light and thermosetting compound, in a total of 100% by weight of the first photocurable compound, the second photocurable compound, and the light and thermosetting compound, The content of the first photocurable compound is 70 wt% or more and 99.9 wt% or less, and the content of the second photocurable compound is 0.1 wt% or more and 30 wt% or less. The manufacturing method of the electronic component of Claim 1 or 2. The adhesive has photocurability and thermosetting;
The adhesive comprises a light and thermosetting compound and a thermosetting agent;
The manufacturing method of the electronic component of any one of Claims 1-3 provided with the heating process which heats the said adhesive agent.   The method for producing an electronic component according to claim 4, wherein the light and thermosetting compound includes a light and thermosetting compound having one or more (meth) acryloyl groups and one or more cyclic ether groups. .   The manufacturing method of the electronic component of Claim 4 or 5 with which the said optical and thermosetting compound contains 4-hydroxybutyl acrylate glycidyl ether.   The first electronic component body is a semiconductor element or a support member for mounting a semiconductor element, and the second electronic component body is a semiconductor element, or the first electronic component body is The manufacturing method of the electronic component of any one of Claims 1-6 which is a semiconductor wafer and whose said 2nd electronic component main body is a cover glass. The adhesive has photocurability and thermosetting;
The first electronic component body is a semiconductor element or a support member for mounting a semiconductor element, and the second electronic component body is a semiconductor element;
Performing the light irradiation step after the coating step, performing the placement step after the light irradiation step,
The manufacturing method of the electronic component of any one of Claims 1-7 provided with the heating process which heats the said adhesive agent irradiated with light after the said arrangement | positioning process. The adhesive has photocurability and thermosetting;
The first electronic component body is a semiconductor wafer, and the second electronic component body is a cover glass;
Performing the light irradiation step after the coating step, performing the placement step after the light irradiation step,
After the placing step, a heating step for heating the adhesive irradiated with light,
The manufacturing method of the electronic component of any one of Claims 1-8 provided with the cutting process which cut | disconnects the laminated body of the said semiconductor wafer, the said adhesive agent, and the said cover glass after the said heating process.

Images