JP6391545B2 - Ink jet adhesive, semiconductor device manufacturing method, and electronic component - Google Patents

Description

  The present invention relates to an inkjet adhesive that is applied and used by an inkjet apparatus. The present invention also relates to a method for manufacturing a semiconductor device using the adhesive, and an electronic component using the adhesive.

  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.

  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.

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

  Conventional adhesives such as those described in Patent Documents 2 and 3 have low storage stability and may increase viscosity during storage. Furthermore, in the conventional adhesive, the adhesiveness after bonding may become low.

  With conventional adhesives, it is difficult to achieve both excellent storage stability and excellent adhesiveness.

  The objective of this invention is providing the adhesive agent for inkjets which is excellent in storage stability and excellent in adhesiveness after hardening. Another object of the present invention is to provide a method for manufacturing a semiconductor device using the adhesive and an electronic component using the adhesive.

  According to a wide aspect of the present invention, there is provided an adhesive used by being applied by an ink jet apparatus, which has a first thermosetting compound having one cyclic ether group and one cyclic ether group, and photoreaction. 100% by weight of an adhesive comprising at least one of a light and thermosetting compound having at least one curable functional group, a second thermosetting compound having at least two cyclic ether groups, and a thermosetting agent. Among them, an adhesive for inkjet (hereinafter sometimes referred to as an adhesive) is provided, wherein the content of the second thermosetting compound is 0.1 wt% or more and 10 wt% or less.

  In a specific aspect of the adhesive according to the present invention, in 100% by weight of the adhesive, the first thermosetting compound, the light and thermosetting compound, and the second thermosetting compound The total content is 35% by weight or more.

  In a specific aspect of the adhesive according to the present invention, the second thermosetting compound includes a thermosetting compound having a polycyclic alicyclic skeleton and having two or more cyclic ether groups.

  In a specific aspect of the adhesive according to the present invention, the adhesive does not include or includes the first thermosetting compound, includes the light and the thermosetting compound, and includes the light and the thermosetting compound. Includes a light and thermosetting compound having one cyclic ether group and one or more (meth) acryloyl groups.

  In a specific aspect of the adhesive according to the present invention, the light and thermosetting compound contains 4-hydroxybutyl acrylate glycidyl ether.

  On the specific situation with the adhesive which concerns on this invention, the said adhesive contains a photocurable compound and a photoinitiator.

  In a specific aspect of the adhesive according to the present invention, the photocurable compound includes a first photocurable compound having one (meth) acryloyl group and a second having two or more (meth) acryloyl groups. And a photocurable compound.

  According to a wide aspect of the present invention, a step of applying the above-mentioned inkjet adhesive by an inkjet device on a surface of a semiconductor element mounting support member or semiconductor element, and curing of the adhesive by light irradiation. A step of forming a B-staged adhesive, a step of laminating a semiconductor element on the surface of the B-staged adhesive opposite to the support member or the semiconductor element side, And a step of thermosetting the B-staged adhesive after lamination.

  According to a wide aspect of the present invention, a step of applying the above-described inkjet adhesive on the surface of a semiconductor wafer by an inkjet apparatus and curing of the adhesive by light irradiation is performed to form a B-stage adhesive. A step of forming an agent, a step of laminating a cover glass on the surface opposite to the semiconductor wafer side of the B-staged adhesive to obtain a laminated body, and the B-staged adhesive in the laminated body There is provided a method for manufacturing a semiconductor device, comprising: a step of thermally curing the substrate; and a step of cutting the laminated body after the heat curing.

  According to a wide aspect of the present invention, a first electronic component body, a second electronic component body, and an adhesive connecting the first electronic component body and the second electronic component body are provided. Provided is an electronic component in which the adhesive is formed by applying and curing the above-described inkjet adhesive using an inkjet apparatus.

  On the specific situation with the electronic component which concerns on this invention, a said 1st electronic component main body is a supporting member or semiconductor element for semiconductor element mounting, and a said 2nd electronic component main body is a semiconductor element.

  The inkjet adhesive according to the present invention has a first thermosetting compound having one cyclic ether group and one cyclic ether group, and light and thermosetting having at least one photoreactive functional group. A content of the second thermosetting compound in 100% by weight of the adhesive, comprising at least one of the compounds, a second thermosetting compound having two or more cyclic ether groups, and a thermosetting agent. Is 0.1 wt% or more and 10 wt% or less, the storage stability of the adhesive can be increased, and the adhesiveness can be increased after curing.

FIG. 1 is a front sectional view schematically showing an electronic component obtained by using the inkjet adhesive according to one 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.

  The inkjet adhesive according to the present invention (hereinafter sometimes referred to as an adhesive) is used by being applied by an inkjet apparatus. The adhesive according to the present invention is different from an adhesive applied by screen printing, an adhesive applied by a dispenser, and the like.

  The adhesive according to the present invention has thermosetting properties. The adhesive according to the present invention may have photocurability or may not have photocurability.

  The adhesive according to the present invention includes a first thermosetting compound having one cyclic ether group and a light and thermosetting compound having one cyclic ether group and one or more photoreactive functional groups. And at least one of them, a second thermosetting compound having two or more cyclic ether groups, and a thermosetting agent. The adhesive according to the present invention may contain a first thermosetting compound having one cyclic ether group, a light having one cyclic ether group and one or more photoreactive functional groups. And a thermosetting compound, a first thermosetting compound having one cyclic ether group, a light having one cyclic ether group and one or more photoreactive functional groups, and And a thermosetting compound.

  In 100% by weight of the adhesive according to the present invention, the content of the second thermosetting compound is 0.1% by weight or more and 10% by weight or less.

  In this invention, since said structure is provided, the storage stability of an adhesive agent can be improved. For example, the viscosity is difficult to increase during storage. Furthermore, in this invention, since said structure is provided, adhesiveness can be improved after hardening. In the present invention, both excellent storage stability and excellent adhesiveness can be achieved.

  The adhesive according to the present invention is preferably applied in a state heated to 50 ° C. or more and 100 ° C. or less. In this invention, even if it heats to 50 degreeC or more, a viscosity does not rise easily.

At 25 ° C., an inkjet adhesive is irradiated with light having an integrated light amount of 1000 mJ / cm ² so that the illuminance at 365 nm is 100 mW / cm ² to obtain a B-stage product. The elastic modulus at 25 ° C. of the B-staged product is preferably 5.0 × 10 ² Pa or more, more preferably 8.0 × 10 ² Pa or more, preferably 8.0 × 10 ⁴ Pa or less, more preferably 5. 0 × 10 ⁴ Pa or less. When the elastic modulus is equal to or higher than the lower limit, the movement of the semiconductor chip or the like hardly occurs. When the elastic modulus is less than or equal to the above upper limit, the adhesive force after bonding of semiconductor chips and the like is further increased, and the generation of voids is suppressed.

  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 ′).

  Since the adhesive according to the present invention 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 ink-jet adhesive while circulating it.

  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 cured adhesive can be formed with high accuracy. Further, in the present invention, even a hardened adhesive layered can be formed finely and with high accuracy.

  The said adhesive agent is used suitably for adhesion | attachment of an electronic component main body.

  The method of manufacturing a semiconductor device according to the present invention includes a step of applying the inkjet adhesive on the surface of a semiconductor element mounting support member or semiconductor element by an inkjet device, and curing of the adhesive by light irradiation. To form a B-staged adhesive, to stack a semiconductor element on the surface of the B-staged adhesive opposite to the support member or the semiconductor element side, and the semiconductor element And the step of thermally curing the B-staged adhesive.

  In addition, the method for manufacturing a semiconductor device according to the present invention includes a step of applying the inkjet adhesive on the surface of a semiconductor wafer by an inkjet device, and curing of the adhesive by light irradiation. A step of forming a staging adhesive; a step of laminating a cover glass on the surface of the B-staging adhesive opposite to the semiconductor wafer side to obtain a laminate; and the B stage in the laminate A step of heat-curing the adhesive, and a step of cutting the laminate after the heat-curing.

  If the adhesive which concerns on this invention is used, the thickness precision of the hardened | cured adhesive can be improved and it can make it hard to produce a void in the hardened | cured adhesive. Therefore, the adhesive according to the present invention can be suitably used in the method for manufacturing a semiconductor device according to the present invention.

  The electronic component according to the present invention includes a first electronic component main body, a second electronic component main body, an adhesive connecting the first electronic component main body and the second electronic component main body, and Is provided. In this electronic component, the adhesive is formed by applying and curing the inkjet adhesive using an inkjet apparatus.

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

  FIG. 1 is a front sectional view schematically showing an electronic component obtained by using the inkjet adhesive according to one 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 the present embodiment, the adhesive 3 is a cured adhesive. In order to form the adhesive 3, the above-described inkjet adhesive is 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 inkjet adhesive is applied on the first electronic component 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, after the application step, the adhesive 12 is irradiated with light from the first light irradiation unit 13 to advance the curing of the adhesive 12 ( First light irradiation step). Thereby, the adhesive 12 </ b> A irradiated with light by the first light irradiation unit 13 is formed. The adhesive 12A is a precured product and is a B-staged adhesive. The elastic modulus at 25 ° C. of the B-staged adhesive is preferably 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. From the viewpoint of further improving the curability of the adhesive, it is preferable that the irradiation intensity irradiated from the second light irradiation unit 14 is stronger than the irradiation intensity of the light irradiated from the first light irradiation unit 13. 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. .

  In addition, “irradiating the adhesive 12 with light from the first light irradiating unit 13 to advance the curing of the adhesive 12” includes advancing the reaction to obtain 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 is irradiated with light to further advance the curing of the adhesive 12A (second light irradiation step). 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 1.0 × 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 1.0 × 10 ² Pa or more. It is more preferable to set it to 8.0 × 10 ⁴ Pa or less.

  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). 1 A of primary laminated bodies are heated, the adhesive agent 12B between the 1st electronic component main body 2 and the 2nd electronic component main body 4 is hardened, and an electronic component is obtained (heating process). 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 has a first thermosetting compound having one cyclic ether group (a curable compound curable by heating) or one cyclic ether group, and has at least one photoreactive functional group. A light and thermosetting compound (a curable compound curable by both light irradiation and heating), a second thermosetting compound having two or more cyclic ether groups (a curable compound curable by heating), and And a thermosetting agent. The adhesive preferably contains a photocurable compound (a curable compound that can be cured by light irradiation) and a photopolymerization initiator. The adhesive preferably contains a curing accelerator.

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

(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 thermal cycle and the like, the adhesive has one cyclic ether group. It preferably contains a light and thermosetting compound having at least one photoreactive functional group. From the viewpoint of improving storage stability and adhesiveness in a well-balanced manner and forming a cured adhesive with high accuracy, the light and thermosetting compound has one cyclic ether group and a (meth) acryloyl group. It is preferable to contain the light and thermosetting compound which have 1 or more. 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, the first thermosetting compound, and the second thermosetting compound are the light and thermosetting compound. It is preferable that it is mix | blended as a component different from.

  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 improving the storage stability and adhesiveness in a well-balanced manner, further increasing the thickness accuracy of the cured adhesive, and further making voids less likely to occur in the cured adhesive, the light and thermosetting compounds are: It 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 is preferably 0% by weight or more, more preferably 0% by weight in 100% by weight of the adhesive. More, more preferably 0.5% by weight or more, particularly preferably 1% 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 first thermosetting compound having one cyclic ether group and a second thermosetting compound having two or more cyclic ether groups.

  In the present invention, of the first thermosetting compound having one cyclic ether group and the light and thermosetting compound having one cyclic ether group and one or more photoreactive functional groups. At least one is used. In the present invention, the second thermosetting compound is essential.

  From the viewpoint of forming the cured adhesive with higher accuracy, a first thermosetting compound having one cyclic ether group is preferably 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 1st 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 effectively increasing the adhesiveness, the second thermosetting compound preferably has a polycyclic alicyclic skeleton.

  From the viewpoint of further suppressing voids and further improving adhesion, moisture-resistant adhesion reliability, and cooling cycle reliability, the thermosetting compound 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 is preferably 25 ° C. or higher, more preferably 30 ° C. or higher, further 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 is preferably 150 ° C. or lower.

  The softening point can be measured according to JIS K7234.

  In 100% by weight of the adhesive, the total content of the first thermosetting compound and the light and thermosetting compound is preferably 25% by weight or more, more preferably 30% by weight or more, preferably 80%. % By weight or less, more preferably 70% by weight or less. When the total content of the first thermosetting compound and the light and thermosetting compound is not less than the above lower limit, the storage stability of the adhesive is further increased, and the adhesive force after thermosetting is more It gets even higher.

  In 100% by weight of the adhesive, the content of the second thermosetting compound is preferably 0.5% by weight or more, more preferably 1% by weight or more, preferably 9% by weight or less, more preferably 8% by weight. % Or less. When the content of the second thermosetting compound is not more than the above upper limit, the storage stability of the adhesive is further enhanced.

  From the viewpoint of further increasing the adhesive strength after thermosetting, the total of the first thermosetting compound, the light and thermosetting compound, and the second thermosetting compound in 100% by weight of the adhesive. The content is preferably 35% by weight or more, more preferably 40% by weight or more.

(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 forming the cured adhesive with higher accuracy, the photocurable compound preferably has a (meth) acryloyl group (one or more). As for the said photocurable compound, only 1 type may 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.

  As the photocurable compound, a photocurable compound having one (meth) acryloyl group (referred to as a first photocurable compound (A1)) may be used, and it has two or more (meth) acryloyl groups. A photocurable compound (referred to as a second photocurable compound (A2)) may be used. 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 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.

  From the viewpoint of further suppressing voids and further improving the adhesiveness, moisture-resistant adhesion reliability, and cooling cycle reliability, the photocurable compound includes the first photocurable compound (A1) and the second photocurable compound. (A2) is preferably contained. Moreover, the hardened adhesive agent can be formed with high accuracy by using the first photocurable compound (A1) and the second photocurable compound (A2) in combination as the photocurable compound. .

  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.

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

  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 content of the photocurable compound, and the first photocurable compound (A1) and the second photocurable, in 100% by weight of the adhesive. The total content of the compound (A2) 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 preventing voids from being generated in the cured adhesive, the content of the photocurable compound in the 100% by weight of the adhesive and the first light The total content of the curable compound (A1), the light and thermosetting compound, and the second photocurable compound (A2) is particularly preferably 5% by weight or more and 80% by weight or less.

  From the viewpoint of further suppressing voids and further improving adhesion, moisture-resistant adhesion reliability, and cooling cycle reliability, the first photocurable compound (A1), light, thermosetting compound, and second photocurable property are used. Of the total 100% by weight of the compound (A2), the content of the first photocurable compound (A1) is 50% by weight or more and 99.95% by weight or less, and the content of the second photocurable compound (A2) The amount is preferably 0.05% by weight or more and 50% by weight or less, and the content of the first photocurable compound (A1) is 60% by weight or more and 99.9% by weight or less, and the second photocuring. The content of the photocurable compound (A2) is more preferably 0.1 wt% or more and 40 wt% or less, and the content of the first photocurable compound (A1) is 70 wt% or more, 99.5 wt%. %, The content of the second photocurable compound (A2) is 0.5% by weight or more And more preferably 30 wt% or less.

(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 (5) guanidine derivative 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.

(Photopolymerization initiator)
The adhesive does not contain or contains a photopolymerization initiator. When the adhesive contains the light and thermosetting compound, the adhesive preferably contains a 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.

(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.

(Examples 1-4, Reference Example 5, Examples 6-7, Reference Example 8, Example 9, Reference Example 10 and Comparative Examples 1-2)
(Preparation of adhesives A to L)
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 L.

(Evaluation)
(Storage stability (increased viscosity))
Based on JIS K2283, the viscosity η1 at 70 ° C. and 10 rpm of the curable composition immediately after production was measured using a viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.). Next, the curable composition was heated at 70 ° C. for 48 hours. The viscosity η2 at 70 ° C. and 10 rpm of the curable composition after heating was measured. The viscosity increase was determined according to the following criteria.

[Criteria for viscosity increase]
◯: Ratio (η2 / η1) is 1 or more and 1.2 or less ○: Ratio (η2 / η1) exceeds 1.2 and 1.5 or less ×: Ratio (η2 / η1) is 1.5 or more

(Die shear strength after thermosetting)
An adhesive layer was formed on each silicon wafer through the steps shown in FIGS. 2A to 2E in accordance with the electronic component manufacturing method described above. While circulating the adhesive at 70 ° C., the coating step for coating and the first light irradiation step (UV-LED lamp having a main wavelength of 365 nm, 100 mW / cm ² , 0.1 second) are repeated. An adhesive layer of 30 μm was formed and photocured in the second light irradiation step (ultra-high pressure mercury lamp, 100 mW / cm ² , 10 seconds). Thereafter, using a die bonding apparatus on the adhesive layer, a silicon bare chip that is assumed to be a semiconductor chip (length 3 mm × width 3 mm × thickness 750 μm) is pressurized at 110 ° C. under the condition of 0.1 MPa for 1 second, and further at 160 ° C. The adhesive test piece after thermosetting was obtained by putting in an oven and heating for 5 hours. Using a die shear strength measuring device (“Dage series 4000” manufactured by Dage, test temperature: 260 ° C.), the die shear strength of the adhesive test piece after thermosetting was measured.

(Void confirmation of adhesive layer in semiconductor devices)
BGA substrate with a wiring step of 5 μm (thickness 0.3 mm, commercially available solder resist is applied, and 90 places are arranged in 5 rows × 16 columns where 10 mm long × 10 mm wide semiconductor chips are placed. ) Was prepared. In accordance with the electronic component manufacturing method according to the embodiment of the present invention described above, an adhesive layer was formed through the steps shown in FIGS. While circulating the adhesive at 70 ° C., the application step of applying and the first light irradiation step (UV-LED lamp having a main wavelength of 365 nm, 100 mW / cm ² ) were repeated 8 times (total) An adhesive layer having an integrated light quantity of 200 mJ / cm ² ) and a thickness of 30 μm was formed, and photocured in the second light irradiation step (ultra-high pressure mercury lamp, 100 mW / cm ² , 10 seconds). Thereafter, a silicon bare chip as a semiconductor chip (10 mm long × 10 mm wide × 80 μm thick) was laminated on the adhesive layer at 80 ° C. and 0.05 MPa using a die bonding apparatus to obtain a laminate. . After laminating the silicon bare chip, it was confirmed using an optical microscope (“Digital Microscope VH-Z100” manufactured by Keyence Corporation) that the protrusion of the adhesive layer was less than 100 μm. The obtained laminated body was put in an oven at 170 ° C. and heated for 2 hours to be thermally cured, thereby obtaining 90 semiconductor devices (laminated structure).

  Using an ultrasonic exploration imaging device (“mi-scope hyper II” manufactured by Hitachi Construction Machinery Finetech Co., Ltd.), voids in the adhesive layer in the obtained semiconductor device were observed and evaluated according to the following criteria.

[Void judgment criteria]
○○: Voids are hardly observed ○: Voids are slightly observed (no problem in use)
X: Void is observed (use problem)

(Moisture absorption reflow of semiconductor devices + reliability test for thermal cycle)
The semiconductor devices (90 pieces) obtained by the evaluation of void confirmation were allowed to stand at 85 ° C. and a humidity of 85 RH% for 168 hours to absorb moisture. Then, it was passed through a solder reflow furnace (preheat 150 ° C. × 100 seconds, reflow [maximum temperature 260 ° C.]) for 5 cycles. The semiconductor device subjected to the moisture absorption reflow test was held at −55 ° C. for 5 minutes using a liquid tank thermal shock tester (“TSB-51” manufactured by ESPEC), then heated to 150 ° C. and 150 ° C. Then, a cooling cycle reliability test was conducted in which the process of holding at 5 minutes and then lowering the temperature to −50 ° C. was 1 cycle. The semiconductor device was taken out after 250 cycles and 500 cycles, and using an ultrasonic exploration imaging device ("mi-scope hyper II" manufactured by Hitachi Construction Machinery Finetech Co., Ltd.), the peeling of the adhesive layer of the semiconductor device was observed. Evaluated by criteria.

[Moisture absorption reflow + Cryogenic cycle reliability test criteria]
○○: Not peeled ○: Slightly peeled (no problem in use)
×: Exfoliated greatly (problems in use)

  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 adhesive used by being applied by an inkjet device,
At least one of a first thermosetting compound having one cyclic ether group and one light and thermosetting compound having one cyclic ether group and one or more photoreactive functional groups;
A second thermosetting compound having two or more cyclic ether groups;
A photocurable compound;
A thermosetting agent ;
A photopolymerization initiator ,
The adhesive 100 wt%, the second content of the thermosetting compound is 0.1 wt% or more state, and are 10 wt% or less, the content of the photocurable compound is 5 wt% or more, 80 wt % der Ru, inkjet adhesive below. The inkjet adhesive according to claim 1, wherein the second thermosetting compound includes a thermosetting compound having a polycyclic alicyclic skeleton and having two or more cyclic ether groups. Not including or including the first thermosetting compound;
Including the light and thermosetting compounds;
The inkjet adhesive according to claim 1 or 2 , wherein the light and thermosetting compound includes a light and thermosetting compound having one cyclic ether group and one or more (meth) acryloyl groups. . The inkjet adhesive of claim 3 , wherein the light and thermosetting compound comprises 4-hydroxybutyl acrylate glycidyl ether. The said photocurable compound contains the 1st photocurable compound which has one (meth) acryloyl group, and the 2nd photocurable compound which has two or more (meth) acryloyl groups . 5. The inkjet adhesive according to any one of 4 above. Applying the inkjet adhesive according to any one of claims 1 to 5 on the surface of the semiconductor element mounting support member or the semiconductor element by an inkjet device;
A step of curing the adhesive by light irradiation to form a B-staged adhesive;
A step of laminating a semiconductor element on the surface opposite to the support member or the semiconductor element side of the B-staged adhesive;
And a step of thermosetting the B-staged adhesive after the semiconductor elements are stacked. The process of apply | coating the adhesive agent for inkjets of any one of Claims 1-5 with the inkjet apparatus on the surface of a semiconductor wafer,
A step of curing the adhesive by light irradiation to form a B-staged adhesive;
Laminating a cover glass on the surface opposite to the semiconductor wafer side of the B-staged adhesive to obtain a laminate;
Thermally curing the B-staged adhesive in the laminate,
And a step of cutting the laminate after thermosetting. A first electronic component main body, a second electronic component main body, and an adhesive connecting the first electronic component main body and the second electronic component main body,
An electronic component in which the adhesive is formed by applying and curing the inkjet adhesive according to any one of claims 1 to 5 using an inkjet apparatus. The first electronic component main body is a supporting member or a semiconductor element for mounting a semiconductor element;
The electronic component according to claim 8 , wherein the second electronic component main body is a semiconductor element.

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