JP6411184B2 - INK JET LIGHT AND THERMOSETTING ADHESIVE, SEMICONDUCTOR DEVICE MANUFACTURING METHOD, AND ELECTRONIC COMPONENT MANUFACTURING METHOD - Google Patents

Description

  The present invention relates to an inkjet light and a thermosetting adhesive that are used by being applied using an inkjet apparatus and are cured by heating after being cured by light irradiation. 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. 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 joining 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. However, such an adhesive has a problem that the tack after photocuring is low, the adhesiveness when a semiconductor chip is attached is low, and extremely minute peeling occurs at the time of thermosetting, resulting in low reliability.

Japanese Patent Laid-Open No. 3-192178 WO11 / 058998A1

  An object of the present invention is to use an ink-jet device to form an adhesive layer with high accuracy, which is applied and used by being cured by heating after being cured by light irradiation and cured by heating. It is an object of the present invention to provide an inkjet light and a thermosetting adhesive capable of making it difficult for voids to be generated in an adhesive layer. 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, an adhesive used by being applied using an ink jet apparatus and cured by heating after being cured by irradiation with light, comprising a photocurable compound, A B-stage comprising a thermosetting compound, a photocuring initiator, and a thermosetting agent, and irradiated with light having an integrated light quantity of 1000 mJ / cm ² so that the illuminance at 365 nm is 100 mW / cm ² at 25 ° C. Provided is an inkjet light and a thermosetting adhesive in which the surface of the adhesive has a tack of 294 mN / cm ² or more at 25 ° C.

  In a specific aspect of the adhesive according to the present invention, the photocurable compound includes a photocurable compound having one photocurable reactive group, and a photocurable compound having two or more photocurable reactive groups. including.

  On the specific situation with the adhesive agent which concerns on this invention, the said photocurable compound which has one photocurable reactive group contains 2-ethylhexyl (meth) acrylate.

  In a specific aspect of the adhesive according to the present invention, the adhesive includes light and a thermosetting compound.

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

  In a specific aspect of the adhesive according to the present invention, the viscosity at 25 ° C. and 10 rpm measured in accordance with JIS K2283 is 160 mPa · s or more and 1600 mPa · s or less.

  On the specific situation with the adhesive which concerns on this invention, when the said adhesive does not contain or contains a solvent and the said adhesive contains the said solvent, content of the said solvent is 1 weight% or less.

  On the specific situation with the adhesive which concerns on this invention, when the said adhesive does not contain or contains a filler and the said adhesive contains the said filler, content of the said filler is 1 weight% or less.

  According to a wide aspect of the present invention, the above-described inkjet light and thermosetting adhesive are applied to the surface of the supporting member for mounting an optical semiconductor element or the semiconductor element using an inkjet apparatus, and an adhesive layer is formed. A step of forming a B-staged adhesive layer by proceeding with curing of the adhesive layer by light irradiation, and the supporting member or the semiconductor element side of the B-staged adhesive layer There is provided a method for manufacturing a semiconductor device, comprising: a step of laminating a semiconductor element on a surface opposite to the step; and a step of thermally curing the B-staged adhesive layer after the lamination of the semiconductor element.

  According to a wide aspect of the present invention, on the surface of a semiconductor wafer, using an inkjet apparatus, the above-described inkjet light and a thermosetting adhesive are ejected to form an adhesive layer; A step of forming a B-staged adhesive layer by proceeding with curing of the adhesive layer by irradiation, and laminating a cover glass on the surface opposite to the semiconductor wafer side of the B-staged adhesive layer. Thus, there is provided a method for manufacturing a semiconductor device, comprising: a step of obtaining a laminated body; a step of thermally curing the B-staged adhesive layer in the laminated body; and a step of cutting the laminated body after thermosetting. .

In a specific aspect of the method for manufacturing a semiconductor device according to the present invention, the tack of the surface of the B-staged adhesive layer at 25 ° C. is set to 294 mN / cm ² or more.

  In a specific aspect of the method for manufacturing a semiconductor device according to the present invention, the ink jet device is connected to the ink tank in which the ink jet light and the thermosetting adhesive are stored, and is connected to the ink tank. A discharge portion for discharging the light for use and the thermosetting adhesive, one end connected to the discharge portion, the other end connected to the ink tank, and the inside for the ink jet light and thermosetting A circulation flow path portion through which an adhesive flows, and in the coating step, after the ink jet light and the thermosetting adhesive are moved from the ink tank to the discharge portion in the ink jet apparatus, the discharge The inkjet light and the thermosetting adhesive that have not been ejected from the flow section are allowed to flow through the circulation flow path section and be moved to the ink tank. Accordingly, while circulating the ink jet optical and thermosetting adhesive is applied.

  On the specific situation with the manufacturing method of the semiconductor device which concerns on this invention, the temperature of the said light for inkjet and the thermosetting adhesive currently circulated is 40 degreeC or more and 100 degrees C or less.

  According to a wide aspect of the present invention, a first electronic component main body, a second electronic component main body, an adhesive layer connecting the first electronic component main body and the second electronic component main body, and The adhesive layer is formed by applying the above-described inkjet light and thermosetting adhesive using an inkjet apparatus, and curing by heating and then curing by light irradiation. An electronic component is provided.

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

The inkjet light and thermosetting adhesive according to the present invention includes a photocurable compound, a thermosetting compound, a photocuring initiator, and a thermosetting agent, and the illuminance at 365 nm is 100 mW at 25 ° C. / so cm tack ² to become like a light accumulated light quantity 1000 mJ / cm ² at 25 ° C. of the irradiated surface of the B-stage adhesive is 294MN / cm ² or more, jet light and heat according to the present invention When a curable adhesive is applied using an ink jet device and cured by light irradiation and then cured by heating, an adhesive layer in which the adhesive is cured is formed with high accuracy. Voids can be made difficult to occur.

FIG. 1 is a front cross-sectional view schematically showing an electronic component obtained using an inkjet light and a thermosetting adhesive 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 cross-sectional view schematically showing a first modification of an electronic component obtained by using the inkjet light and the thermosetting adhesive according to an embodiment of the present invention. FIG. 7 is a front cross-sectional view schematically showing a second modification of the electronic component obtained by using the inkjet light and the thermosetting adhesive according to one embodiment of the present invention.

  Hereinafter, the present invention will be described in detail.

  The inkjet light and thermosetting adhesive (hereinafter sometimes abbreviated as adhesive) according to the present invention are used by being applied using 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 is used after being cured by heating and then cured by heating. The adhesive according to the present invention is a light and thermosetting adhesive, and has photocurability and thermosetting. The adhesive according to the present invention is different from an adhesive in which only photocuring is performed, an adhesive in which only thermosetting is performed, and the like.

  The adhesive according to the present invention includes a photocurable compound (a curable compound that can be cured by light irradiation), a thermosetting compound (a curable compound that can be cured by heating), a photopolymerization initiator, and thermosetting. Agent.

The adhesive according to the present invention has a 25 ° C. tack on the surface of the B-staged adhesive that has been irradiated with light with an integrated light quantity of 1000 mJ / cm ² so that the illuminance at 365 nm is 100 mW / cm ² at 25 ° C. 294 mN / cm ² or more.

  Since the adhesive according to the present invention has the above-described configuration, the inkjet light and the thermosetting adhesive according to the present invention are applied using an inkjet apparatus, and then the curing proceeds by light irradiation. Then, when cured by heating, an adhesive layer in which the adhesive is cured can be formed with high accuracy, and voids can be hardly formed in the adhesive layer. Moreover, in this invention, a hygroscopic property and a thermal cycle characteristic can also be made favorable.

The tack of the surface of the B-staged adhesive at 25 ° C. is 294 mN / cm ² or more, preferably 490 mN / cm ² or more. When the tack is not less than the lower limit, the position accuracy of the semiconductor element is further improved.

With the above tack, a probe tacking tester manufactured by Reska Co., Ltd., probe: made of SUS and diameter 5.0 mm, peeling speed: 10 mm / second, contact load: 980 mN / cm ² (100 gf / cm ² ), and The contact time is a value measured at 25 ° C. under the condition of 1 second.

  Since the adhesive according to the present invention is applied using an inkjet apparatus, it 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 forming the adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, 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.

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

  The method for manufacturing a semiconductor device according to the present invention comprises applying an ink jet light and a thermosetting adhesive to the support member for mounting an optical semiconductor element or the surface of the semiconductor element by using the ink jet apparatus, and applying the adhesive. A coating step for forming a layer; a step of forming a B-staged adhesive layer by curing the adhesive layer by light irradiation; and the support member or the semiconductor element of the B-staged adhesive layer. A step of laminating a semiconductor element on a surface opposite to the side, and a step of thermally curing the B-staged adhesive layer after laminating the semiconductor element.

  Moreover, the manufacturing method of the semiconductor device according to the present invention includes a coating step of forming an adhesive layer on the surface of a semiconductor wafer by ejecting the inkjet light and the thermosetting adhesive using an inkjet device. A step of forming a B-staged adhesive layer by curing the adhesive layer by light irradiation, and a cover glass on the surface opposite to the semiconductor wafer side of the B-staged adhesive layer. Are laminated to obtain a laminate, a step of thermally curing the B-staged adhesive layer in the laminate, and a step of cutting the laminate after thermosetting.

  If the adhesive which concerns on this invention is used, an adhesive bond layer can be formed with high precision and it can be made hard to produce a void in an adhesive bond layer. 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.

  From the viewpoint of forming the adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, it is preferable to apply the ink-jet light and the thermosetting adhesive while circulating them.

  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 adhesive layer can be formed with higher accuracy, and voids can be further hardly generated in the adhesive layer.

  Moreover, in this invention, a thick adhesive bond layer can be formed with high precision. In the present invention, even a multi-layered adhesive layer can be formed finely and with high accuracy.

  Hereinafter, the present invention will be clarified by describing specific embodiments and examples of the present invention with reference to the drawings.

  FIG. 1 is a front cross-sectional view schematically showing an electronic component obtained using an inkjet light and a thermosetting adhesive according to an embodiment of the present invention.

  An electronic component 1 shown in FIG. 1 includes a first electronic component body 2, an adhesive layer 3 disposed on the surface of the first electronic component body 2, and a first disposed on the surface of the adhesive layer 3. 2 electronic component main bodies 4. The second electronic component body 4 is disposed on the opposite side of the adhesive layer 3 from the first electronic component body 2 side. On the first surface of the adhesive layer 3, the first electronic component body 2 is disposed. On the second surface opposite to the first surface of the adhesive layer 3, the second electronic component body 4 is arranged. The adhesive layer 3 is an adhesive layer after light and heat curing, and is a cured adhesive layer. In order to form the adhesive layer 3, the inkjet light and the thermosetting adhesive according to an embodiment of the present invention are used. The ink jet light and the thermosetting adhesive are applied by using an ink jet apparatus, and after being cured by light irradiation, cured by heating to form the adhesive layer 3.

  Specific examples of the electronic component body include a semiconductor wafer, a semiconductor wafer after dicing (divided semiconductor wafer, semiconductor element), a cover glass, a capacitor, a diode, a printed board, a flexible printed board, a glass epoxy board, and glass. Examples include substrates. The electronic component main body may be a support member for mounting an optical semiconductor element.

  Since an adhesive layer formed with high accuracy is particularly required, the electronic component body is preferably a circuit board, a cover glass, a semiconductor wafer, or a semiconductor wafer after dicing.

  Since an adhesive layer formed with high accuracy is particularly required, the first electronic component body is preferably a support member or a semiconductor element for mounting an optical semiconductor element, and is a circuit board or a semiconductor element. Is more preferable, and a circuit substrate or a semiconductor wafer after dicing is more preferable. Since the adhesive layer formed with high precision is particularly required, the second electronic component main body is preferably a semiconductor element, and more preferably a dicing semiconductor wafer.

  Since an adhesive layer formed with high precision is particularly required, the first electronic component body is a circuit board or a semiconductor wafer after dicing, and the second electronic component body is a semiconductor wafer after dicing. Furthermore, it is more preferable that the first electronic component body is a circuit board and the second electronic component body is a semiconductor wafer after dicing. The electronic component is preferably an electronic component for a semiconductor device.

  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 ink jet light and a thermosetting adhesive are applied on the first electronic component body 2 using an ink jet device 11 to form an adhesive layer 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 layer 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 precision of forming a fine adhesive layer by increasing the dischargeability of the adhesive, the inkjet apparatus is an inkjet apparatus using a piezoelectric inkjet head, and the action of the piezoelectric element in the application process. It is preferable to apply the adhesive.

  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 adhesive layer, the circulation channel section preferably includes a pump for transferring the adhesive into the circulation channel section.

  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 layer with higher accuracy, it is preferable that the circulation channel portion includes a buffer tank in which the adhesive is temporarily stored in the circulation channel 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 layer 12 is irradiated with light from the first light irradiation unit 13 and the curing of the adhesive layer 12 proceeds. (First light irradiation step). Thereby, the adhesive layer 12 </ b> A irradiated with light by the first light irradiation unit 13 is formed. The adhesive layer 12A is a pre-cured product and is a B-staged adhesive layer. The tack of the surface of the B-staged adhesive layer at 25 ° C. is preferably 294 mN / cm ² or more. 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 layer, 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 light to the adhesive layer 12 from the first light irradiation unit 13 to advance the curing of the adhesive layer 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 adhesive layer, 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 layer 12A irradiated with light from the light irradiation unit 13 is irradiated with light to further advance the curing of the adhesive layer 12A (second light irradiation step). Thereby, the adhesive layer 12 </ b> B irradiated with light by the second light irradiation unit 14 is formed. The adhesive layer 12B is a pre-cured product and is a B-staged adhesive layer. The tack of the surface of the B-staged adhesive layer at 25 ° C. is preferably 294 mN / cm ² or more. Of the B-staged adhesive layer after the second light irradiation step and the B-staged adhesive layer after the first light irradiation, the B-staged adhesive after the first light irradiation. The tack of the surface of the layer at 25 ° C. is preferably 294 mN / cm ² or more. Tack at 25 ° C. on both surfaces of the B-staged adhesive layer after the second light irradiation step and the B-staged adhesive layer after the first light irradiation is set to 294 mN / cm ² or more. It is more preferable.

  Said 2nd light irradiation process is preferably performed before the lamination process mentioned later, and it is preferable to be performed before a heating process. From the viewpoint of forming the cured adhesive layer with higher accuracy, the second light irradiation step is preferably performed. However, the second light irradiation step is not necessarily performed, and a laminating 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 body 4 is disposed on the adhesive layer 12B irradiated with light. The first electronic component main body 2 and the second electronic component main body 4 are bonded together by applying pressure through the adhesive layer 12B irradiated with light to obtain a primary laminate 1A (lamination step). ). When the second light irradiation step is not performed after the first light irradiation step, the second electronic component body 4 is disposed on the adhesive layer 12A irradiated with light, and the second light irradiation step is performed. The first electronic component body 2 and the second electronic component body 4 are bonded together by applying pressure through the adhesive layer 12A irradiated with light to obtain a primary laminate (lamination step).

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

  Note that the adhesive layer may be multilayered by repeating the coating step and the first light irradiation step to form a multilayer adhesive layer. As shown in FIG. 5, an electronic component 31 including an adhesive layer 32 in which a plurality of adhesive layers 32A, 32B, and 32C are stacked may be obtained.

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

  From the viewpoint of improving the dischargeability of the adhesive and forming the cured adhesive layer with higher accuracy, the viscosity at 10 rpm during discharge of the adhesive is 3 mPa · s or more, more preferably 5 mPa · s or more. More preferably, it is 160 mPa · s or more, preferably 2000 mPa · s or less, more preferably 1600 mPa · s or less, and still more preferably 1500 mPa · s or less. From the viewpoint of forming the adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, the viscosity at 10 rpm when the adhesive is discharged is 160 mPa · s or more and 1600 mPa · s or less. It is particularly preferred.

  The viscosity is measured at an ejection temperature 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 layer with higher accuracy, the pressure applied at the time of bonding is preferably 0.01 MPa or more, more preferably 0.05 MPa or more, preferably 10 MPa or less, in the above-described lamination step. Preferably it is 8 MPa or less.

  From the viewpoint of forming the cured adhesive layer with higher accuracy, 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, in the laminating step. It is 130 degrees C or less.

  The said adhesive agent has photocurability and thermosetting. The adhesive includes a photocurable compound, a thermosetting compound, a photopolymerization initiator, 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). The adhesive preferably contains a curing accelerator.

  Hereinafter, the detail of each component contained in 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 forming the cured adhesive layer 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 the (meth) acryloyl group means a compound having at least one of a methacryloyl group and an acryloyl group.

  As the photocurable compound, a polyfunctional compound (A1) having two or more photoreactive groups may be used, or a monofunctional compound (A2) having one photoreactive group may be used.

  From the viewpoint of forming a cured adhesive layer with higher accuracy, the adhesive contains, as the photocurable compound, a monofunctional compound (A2) having one (meth) acryloyl group and (meth) acryloyl. It is preferable to include a polyfunctional compound (A1) having two or more groups.

  Examples of the polyfunctional compound (A1) include (meth) acrylic acid adducts of polyhydric alcohols, (meth) acrylic acid adducts of alkylene oxide modified products of polyhydric alcohols, urethane (meth) acrylates, and polyesters (meta ) Acrylates and the like. 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.

  Specific examples of the polyfunctional compound (A1) include tricyclodecane dimethanol di (meth) acrylate, isobornyl dimethanol di (meth) acrylate, dicyclopentenyl dimethanol di (meth) acrylate, and the like. Especially, it is preferable that the said polyfunctional compound (A1) is tricyclodecane dimethanol di (meth) acrylate from a viewpoint of improving the heat-and-moisture resistance of hardened | cured material further.

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

  The polyfunctional compound (A1) is preferably a polyfunctional compound (A1) having a polycyclic skeleton and having two or more (meth) acryloyl groups. By using the polyfunctional compound (A1), the heat and moisture resistance of the cured product of the adhesive can be increased. Therefore, the reliability of the electronic component can be increased.

  The polyfunctional compound (A1) is not particularly limited as long as it has a polycyclic skeleton and two or more (meth) acryloyl groups. As the polyfunctional compound (A1), a conventionally known polyfunctional compound having a polycyclic skeleton and having two or more (meth) acryloyl groups can be used. Since the polyfunctional compound (A1) has two or more (meth) acryloyl groups, the polymerization proceeds and is cured by light irradiation. As for the said polyfunctional compound (A1), only 1 type may be used and 2 or more types may be used together.

  Specific examples of the polyfunctional compound (A1) include tricyclodecane dimethanol di (meth) acrylate, isobornyl dimethanol di (meth) acrylate, dicyclopentenyl dimethanol di (meth) acrylate, and the like. Especially, it is preferable that the said polyfunctional compound (A1) is tricyclodecane dimethanol di (meth) acrylate from a viewpoint of improving the heat-and-moisture resistance of hardened | cured material further.

  The “polycyclic skeleton” in the polyfunctional compound (A1) and the monofunctional compound (A2) described later indicates a structure having a plurality of cyclic skeletons continuously. Examples of the polycyclic skeleton in the polyfunctional compound (A1) and the monofunctional compound (A2) 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.

  Specific examples of the monofunctional compound (A2) include 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, dihydroxycyclopentadienyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl. (Meth) acrylate, dicyclopentanyl (meth) acrylate, naphthyl (meth) acrylate, etc. are mentioned. Among these, from the viewpoint of further improving the heat and heat resistance of the cured product, the monofunctional compound (A2) is composed of isobornyl (meth) acrylate, dihydroxycyclopentadienyl (meth) acrylate, dicyclopentenyl (meth) acrylate, di It is preferably at least one selected from the group consisting of cyclopentenyloxyethyl (meth) acrylate and dicyclopentanyl (meth) acrylate.

  Examples of the 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 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-phenylenedimaleimide, 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-tolylene dialeimide, N, N'-2,6-tolylene dialeimide, and N, N'-m-xylylene dimaleimide and the like can be mentioned.

  From the viewpoint of further increasing the insulation reliability and adhesion reliability, the photocurable compound preferably has a dicyclopentadiene skeleton.

  From the viewpoint of forming the adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, the photocurable compound includes a photocurable compound having two or more photocurable reactive groups. It is preferable.

  From the viewpoint of forming the adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, the photocurable compound contains a photocurable compound having one photocurable reactive group. It is preferable that it contains a photocurable compound having one photocurable reactive group and a photocurable compound having two or more photocurable reactive groups.

  The photocurable reactive group is preferably a group containing a polymerizable unsaturated double bond, and more preferably a (meth) acryloyl group.

  From the viewpoint of forming the cured adhesive layer with higher accuracy, it is preferred that the photocurable compound having one photocurable reactive group contains 2-ethylhexyl (meth) acrylate.

  From the viewpoint of forming the cured adhesive layer with higher accuracy, the content of the photocurable compound is preferably 1% by weight or more, more preferably 5% by weight or more, in 100% by weight of the adhesive. Preferably it is 80 weight% or less, More preferably, it is 70 weight% or less. From the viewpoint of forming the adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, the content of the photocurable compound in the adhesive of 100% by weight is 1% by weight or more, It is particularly preferred that it is 70% by weight or less.

  From the viewpoint of forming the adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, the photocurable compound has at least two photocurable reactive groups in 100% by weight of the total. The content of the photocurable compound is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 100% by weight (total amount) or less, more preferably 30% by weight or less, and still more preferably 20% by weight. % Or less.

  From the viewpoint of forming the adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, light having one photocurable reactive group in 100% by weight of the total photocurable compound is used. The content of the curable compound is preferably 1% by weight or more, more preferably 10% by weight or more, preferably 100% by weight (total amount) or less, more preferably 99% by weight or less, and still more preferably 90% by weight or less.

(Light and thermosetting compounds)
From the viewpoint of forming the adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, the adhesive preferably contains light and a thermosetting compound. 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 layer with higher accuracy, the light and thermosetting compound preferably has a (meth) acryloyl group and a cyclic ether group, and a (meth) acryloyl group and an epoxy group. It is preferable to have. As for the said light and a thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  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 forming the cured adhesive layer with higher accuracy, the light and thermosetting compound preferably contains 4-hydroxybutyl acrylate glycidyl ether.

  From the viewpoint of forming the cured adhesive layer with higher accuracy, the content of the light and thermosetting compound and 4-hydroxybutyl acrylate glycidyl ether in 100% by weight of the adhesive is preferably 0.00. It is 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 layer with higher accuracy, the total content of the photocurable compound and the light and thermosetting compound is preferably 10% in 100% by weight of the adhesive. % Or more, 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, a thermosetting compound having a thiirane group, and the like. From the viewpoint of forming the cured adhesive layer with higher accuracy, the thermosetting compound is preferably a thermosetting compound having a cyclic ether group, and a thermosetting compound having an epoxy group (epoxy compound). ) Is more preferable. 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 the adhesive layer with higher accuracy and making it more difficult for voids to be generated in the adhesive layer, the thermosetting compound preferably has an aromatic skeleton.

  From the viewpoint of forming the cured adhesive layer with higher accuracy, the content of the thermosetting compound is preferably 10% by weight or more, more preferably 20% by weight or more, in 100% by weight of the adhesive. Preferably it is 80 weight% or less, More preferably, it is 70 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, benzoin alkyl ethers, acetophenones, aminoacetophenones, anthraquinones, thioxanthones, ketals, 2,4,5-triarylimidazole dimers, Examples include riboflavin tetrabutyrate, thiol compounds, 2,4,6-tris-s-triazine, organic halogen compounds, benzophenones, xanthones, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. 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 photo radical polymerization 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 addition, a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals) having absorption in the visible light region may be used to promote the photoreaction.

  It does not specifically limit as said photocationic polymerization initiator, For example, a sulfonium salt, an iodonium salt, a metallocene compound, a benzoin tosylate etc. are mentioned. As for the said photocationic polymerization initiator, 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. As for the said thermosetting agent, only 1 type may be used and 2 or more types may be used together.

  The amine compound means a compound having one or more primary to tertiary amino groups. Examples of the amine compound include (1) aliphatic polyamines, (2) alicyclic polyamines, (3) aromatic polyamines, (4) hydrazides, and (5) guanidine derivatives. In addition, epoxy compound addition 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 addition Adducts such as 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 polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine.

  Examples of the (2) alicyclic polyamine 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.

  Examples of the aromatic polyamine (3) include m-phenylenediamine, p-phenylenediamine, o-xylenediamine, m-xylenediamine, p-xylenediamine, 4,4-diaminodiphenylmethane, 4,4-diaminodiphenylpropane, 4,4-diaminodiphenylsulfone, 4,4-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5-diaminonaphthalene, 1,1-bis (4-aminophenyl) cyclohexane, 2,2- Bis [(4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,3-bis (4-aminophenoxy) benzene, 4,4-methylene-bis (2-chloro) Aniline), and 4,4-diaminodiphenylsulfone It is.

  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 forming the adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, the thermosetting agent is preferably an acid anhydride.

  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 forming the adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, the lower the solvent content in the adhesive, the better.

  Examples of the solvent include water and organic solvents. Among these, an organic solvent is preferable from the viewpoint of further improving the removability of the residue. 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 forming the adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, 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 obtained by using the inkjet light and the thermosetting adhesive according to an embodiment of the present invention will be described.

  FIG. 6 is a front cross-sectional view schematically showing a first modification of an electronic component obtained by using the inkjet light and the thermosetting adhesive according to an embodiment of the present invention.

  A semiconductor device 71 shown in FIG. 6 is an electronic component. The semiconductor device 71 includes a substrate 53A, an adhesive layer 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 layer 72. The adhesive layer 72 is formed by photocuring and thermosetting 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 cross-sectional view schematically showing a second modification of the electronic component obtained by using the inkjet light and the thermosetting adhesive according to one embodiment of the present invention.

  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 layer 54, and a second semiconductor wafer 55 laminated on the substrate 53 via the adhesive layer 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 layer 54 is formed, for example, by curing a curable composition. The curable composition layer using the curable composition before hardening may have adhesiveness. In order to form the curable composition layer before curing, a curable composition 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 layer 61. The adhesive layer 61 is formed by photocuring and thermosetting 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.

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

  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.

Example 1
(Preparation of adhesive A)
3 parts by weight of tricyclodecane dimethanol diacrylate (“IRR-214K” manufactured by Daicel Ornex Co., Ltd.) as a photocurable compound, 10 parts by weight of lauryl acrylate (“LA” manufactured by Kyoeisha Chemical Co., Ltd.), light and thermosetting 41 parts by weight of 4-hydroxybutyl acrylate glycidyl ether (“4HBAGE” manufactured by Nippon Kasei Co., Ltd.) as a compound, 20 parts by weight of a bisphenol A type epoxy compound (“YD-127” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) as a thermosetting compound, 20 parts by weight of an acid anhydride having a terpene skeleton (“YH306” manufactured by Mitsubishi Chemical Corporation) as a thermosetting agent, 1 part by weight of DBU-octylate (“UCAT SA-102” manufactured by San Apro) as a curing accelerator, and light 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butyl as a polymerization initiator 5 parts by weight of Thanon-1 (“IRGACURE369” manufactured by BASF) were uniformly mixed to obtain an adhesive A.

(Examples 2 to 11 and Comparative Examples 1 and 2)
(Preparation of adhesives B to M)
Adhesives B to M were prepared in the same manner as in the preparation of the adhesive A except that the components shown in Table 1 below were added in the amounts shown in Table 2 below.

(Evaluation)
(Viscosity of adhesive at 25 ° C)
Based on JIS K2283, the viscosity of the adhesive at 25 ° C. and 10 rpm was measured using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.). The viscosity was evaluated according to the following criteria.

[Criteria for viscosity]
○: Viscosity is 160 mPa · s or more and 1600 mPa · s or less ×: Viscosity is less than 160 mPa · s or exceeds 1600 mPa · s

(Tack evaluation)
An adhesive was applied onto the substrate with a spin coater so that the thickness was 20 μm. An exposure apparatus (superhigh pressure mercury lamp, adjusted to have an illuminance at 365 nm of 100 mW / cm ² measured at 25 ° C. with an illuminometer (“UIT-201” manufactured by USHIO INC.) At 25 ° C. The light was irradiated for 10 seconds using “JL-4300-3” manufactured by Oak Manufacturing Co., Ltd. (integrated light quantity: 1000 mJ / cm ² ). Using the probe stage tester manufactured by Reska, the obtained B-staged sample was probe: SUS, diameter 5.0 mm, peeling speed: 10 mm / sec, contact load: 980 mN / cm ² (100 gf / cm ² ) And a contact time of 1 second.

(Confirmation of voids in adhesive layers in semiconductor devices)
FR4 glass epoxy substrate (thickness 0.3 mm, commercially available solder resist is applied, 27 places in 3 rows by 9 columns, where 10 mm long by 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 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. Then, an adhesive layer having 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, on the adhesive layer, a die-bonding apparatus was used to laminate a silicon bare chip as a semiconductor chip (vertical 10 mm × width 10 mm × thickness 80 μm) at 110 ° C. and 0.2 MPa, thereby obtaining 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 laminate was placed in an oven at 160 ° C. and heated for 3 hours to be thermally cured, thereby obtaining 27 semiconductor devices (laminated structures).

  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]
○○: Little void was observed ○: Slight void was observed (no problem in use)
X: Void was observed (use problem)

(Confirmation of protruding adhesive layer in semiconductor devices)
Using an optical microscope ("Digital Microscope VH-Z100" manufactured by Keyence Corporation), the protrusion of the adhesive layer of the semiconductor device obtained by the evaluation of void confirmation was observed and evaluated according to the following criteria.

[Extrusion criteria]
○○: Almost no protrusion was observed (the protrusion distance was less than 100 μm)
○: The protrusion was not observed so much (the protrusion distance was 100 μm or more and less than 200 μm)
X: The protrusion was observed (the protrusion amount distance was 200 μm or more).

(Moisture absorption reflow of semiconductor devices + reliability test for thermal cycle)
The semiconductor devices (27 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 1 cycle and 3 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 test was performed in which the process of holding the temperature for 5 minutes and then lowering the temperature to −50 ° C. was taken as one cycle. Take out the semiconductor device after 250 cycles, 500 cycles and 1000 cycles, and observe the peeling of the adhesive layer of the semiconductor device using an ultrasonic exploration imaging device (“mi-scope hyper II” manufactured by Hitachi Construction Machinery Finetech Co., Ltd.). The evaluation was based on the following criteria.

[Criteria for moisture reflow + cooling cycle evaluation]
○○: 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 layer (after heating)
4 ... 2nd electronic component main body 11, 11X ... Inkjet device 12 ... Adhesive layer 12A ... Adhesive layer irradiated with light by first light irradiation unit 12B ... Light was irradiated by second light irradiation unit Adhesive layer 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 layer (after heating)
32A, 32B, 32C ... Adhesive layer (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 layer 55 ... 2nd semiconductor wafer 55a, 73a ... Connection terminal 56, 63, 74 ... Wiring 62, 73 ... First semiconductor wafer 62a ... Connection terminal

Claims (14)

An adhesive used by being applied using an ink jet device and cured by heating after being cured by light irradiation,
A photo-curable compound having a (meth) acryloyl group (excluding a compound having an epoxy group ) , a thermosetting compound having an epoxy group (excluding a compound having a (meth) acryloyl group) , and (meta ) A light and thermosetting compound having an acryloyl group and an epoxy group, a photocuring initiator, and a thermosetting agent,
At 25 ° C., the tack of the surface of the B-staged adhesive irradiated with light having an integrated light quantity of 1000 mJ / cm ² so that the illuminance at 365 nm is 100 mW / cm ² is 294 mN / cm ² or more. Ink-jet light and thermosetting adhesives. The photocurable compound, (meth) light curable compound having one acryloyl group, (meth) acryloyl group and a photocurable compound having two or more, and jet beam according to claim 1 Thermosetting adhesive. The light and thermosetting adhesive for inkjet according to claim 2, wherein the photocurable compound having one (meth) acryloyl group contains 2-ethylhexyl (meth) acrylate. The inkjet light and thermosetting adhesive according to any one of claims 1 to 3, wherein the light and thermosetting compound comprises 4-hydroxybutyl acrylate glycidyl ether. Viscosity at 25 ° C. and 10rpm which was measured according to JIS K2283 is 160 mPa · s or more, or less 1600 · s, claim 1 jet beam and thermosetting adhesive of any one of 4 Agent. Contains or does not contain solvent,
When including the solvent, the content of the solvent is less than 1 wt%, jet beam and thermosetting adhesive according to any one of claims 1-5. Does not contain filler or contains
When containing the filler, the content of the filler is less than 1 wt%, jet beam and thermosetting adhesive according to any one of claims 1-6. On the surface of the support member or a semiconductor element for mounting semi-conductor elements, using an inkjet device, by applying an inkjet light and thermosetting adhesive according to any one of claims 1 to 7 bonded An application process for forming the agent layer;
Curing the adhesive layer by irradiation with light to form a B-staged adhesive layer;
Laminating a semiconductor element on the surface opposite to the support member or the semiconductor element side of the B-staged adhesive layer;
And a step of thermosetting the B-staged adhesive layer after the semiconductor elements are stacked. On the surface of a semiconductor wafer, using an ink jet device, the ink jet light and thermosetting adhesive according to any one of claims 1 to 7 are ejected to form an adhesive layer; and
Curing the adhesive layer by irradiation with light to form a B-staged adhesive layer;
Laminating a cover glass on the surface opposite to the semiconductor wafer side of the B-staged adhesive layer to obtain a laminate;
Thermally curing the B-staged adhesive layer in the laminate;
And a step of cutting the laminate after thermosetting. The method for manufacturing a semiconductor device according to claim 8 or 9 , wherein a tack of the surface of the B-staged adhesive layer at 25 ° C is set to 294 mN / cm ² or more. An ink tank in which the inkjet light and the thermosetting adhesive are stored; an ejection unit connected to the ink tank and from which the inkjet light and the thermosetting adhesive are ejected; One end is connected to the ejection part, the other end is connected to the ink tank, and the inside has a circulation flow path part through which the inkjet light and the thermosetting adhesive flow,
In the coating step, the inkjet light and the thermosetting which are not ejected from the ejection unit after the inkjet light and the thermosetting adhesive are moved from the ink tank to the ejection unit in the inkjet apparatus. sex adhesive, by moving the ink tank by flowing the circulation flow path portion, while circulating the ink jet optical and thermosetting adhesive is applied, any one of claims 8-10 The manufacturing method of the semiconductor device as described in any one of. The method of manufacturing a semiconductor device according to claim 11 , wherein the temperature of the inkjet light and the thermosetting adhesive that are circulated are 40 ° C. or higher and 100 ° C. or lower. In a first electronic component body, and a second electronic component body, wherein the first electronic component main body and the second electronic component body and the electronic component manufacturing method Ru and an adhesive layer connecting the There,
The 請 Motomeko 1-7 jet beam and thermosetting adhesive of any one of, was applied using an inkjet device, and is cured by heating was allowed to proceed curing by light irradiation, Ru comprising a step of forming the adhesive layer, a method of manufacturing an electronic component. The first electronic component body is a support member or a semiconductor element for mounting semi-conductor elements,
The method of manufacturing an electronic component according to claim 13 , wherein the second electronic component main body is a semiconductor element.

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