JP2015229758A - Light-and-heat-curable adhesive for inkjet, production method of electronic part and electronic part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light-and-heat-curable adhesive for inkjet which enables high-accuracy formation of an adhesive layer with the adhesive hardened and suppresses formation of voids in the adhesive layer.SOLUTION: A light-and-heat-curable adhesive is used by application with an inkjet device. The adhesive is used by irradiating with light to promote hardening and then hardening by heating, comprises a photo-curable compound, a thermosetting compound, a photopolymerization initiator and a thermosetting agent and contains a thermosetting agent of formula (1) as the thermosetting agent. In formula (1), R1 to R15 are individually a hydrogen atom, an allyl group or 1-18C alkyl group; n is an integer of 0-10.

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 an electronic component using the adhesive and an electronic component using the adhesive.

  A semiconductor device in which a semiconductor chip is laminated on a substrate via a cured product layer is known. A semiconductor device in which a plurality of semiconductor chips are stacked via a cured product layer is widely known.

  In the semiconductor device, the semiconductor chip with the curable composition layer is placed on the substrate or the semiconductor chip from the curable composition layer side in a state where the curable composition layer (adhesive layer) is laminated on the lower surface of the semiconductor chip. It is manufactured by laminating and curing a curable composition layer. An example of a method for manufacturing such a semiconductor device is disclosed in Patent Document 1 below, for example. Moreover, in patent document 1, in order to form the said curable composition layer (adhesive layer), the composition containing a radiation polymerizable compound, a photoinitiator, and a thermosetting resin is disclosed. .

  In addition, for example, the semiconductor device forms a curable composition layer by applying a curable composition on a substrate or a semiconductor chip by a dispenser or screen printing, and then stacks the semiconductor chip on the curable composition layer. In some cases, the curable composition layer is cured.

  Another example of a method for manufacturing a printed wiring board is disclosed in Patent Document 2 below. In Patent Document 2, a resist material, which is a photocurable thermosetting composition for inkjet, is ejected from an inkjet device onto a substrate to cure the resist material.

WO2011 / 058996A1 WO2004 / 099272A1

  In the above-described conventional method for manufacturing a semiconductor device, the thickness accuracy tends to be low, and the adhesive layer may protrude or flatness may not be obtained, so that voids may occur. Therefore, the adhesion reliability between the layers in the semiconductor device may be lowered.

  In particular, in the production method in which the curable composition is applied by dispenser or screen printing, there is a problem that it is difficult to apply the curable composition with a uniform thickness.

  Moreover, the viscosity of the curable composition for inkjet described in Patent Document 2 is relatively low. For this reason, the curable composition for inkjet described in Patent Document 2 can be applied onto a substrate by an inkjet method.

  By using an inkjet method, it is possible to produce a semiconductor device with high thickness accuracy and no voids. However, even if the composition described in Patent Document 2 is used, the adhesive layer may not be formed with high accuracy.

  Moreover, the curable composition for inkjet described in Patent Document 2 has a problem that the pot life under an environment of 50 ° C. or higher is short. For example, when an inkjet curable composition is ejected by an inkjet device, the inkjet curable composition generally remains in the inkjet device for a certain period of time after being supplied into the inkjet device. On the other hand, the temperature in the ink jet apparatus may be heated to 50 ° C. or higher in order to improve the ejection property. In the curable composition for inkjet described in Patent Document 2, the composition is cured in an inkjet apparatus heated to 50 ° C. or more, and the viscosity of the composition increases, and the composition is discharged. It can be difficult.

  The object of the present invention is to be used by being applied using an ink jet device, and to be cured by heating after being cured by light irradiation, can suppress gelation and enhance storage stability, It is another object of the present invention to provide an inkjet light and a thermosetting adhesive capable of forming an adhesive layer cured with an adhesive with high accuracy and making it difficult to form voids in the adhesive layer. Another object of the present invention is to provide a method for producing an electronic component 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, An inkjet light and a thermosetting adhesive, which includes a thermosetting compound, a photopolymerization initiator, and a thermosetting agent, and includes a thermosetting agent represented by the following formula (1) as the thermosetting agent. Provided.

  In said formula (1), R1-R15 respectively represents a hydrogen atom, an allyl group, or a C1-C18 alkyl group, and n represents the integer of 0-10.

  In a specific aspect of the adhesive according to the present invention, the thermosetting agent represented by the formula (1) measured in accordance with JIS K2283 has a viscosity of 1 Pa · s to 50 Pa · s at 25 ° C. and 1 rpm. It is as follows.

  In a specific aspect of the adhesive according to the present invention, a viscosity at 1 rpm at 25 ° C. 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, the said photocurable compound contains the photocurable compound represented by following formula (11).

  In the formula (11), R1 and R2 each represent a hydrogen atom or a methyl group.

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

  On the specific situation with the adhesive which concerns on this invention, the said light and a thermosetting compound are the light and a thermosetting compound represented by following formula (21).

  In said formula (21), R represents a hydrogen atom or a methyl group.

  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, an application step of applying an inkjet light and a thermosetting adhesive as described above to form an adhesive layer on the surface of the first electronic component body using an inkjet apparatus. And after the coating step, irradiate the adhesive layer with light to advance the curing of the adhesive layer, and after the light irradiation step, on the adhesive layer irradiated with light, A second electronic component main body is disposed, and the first electronic component main body and the second electronic component main body are bonded together by applying pressure via the adhesive layer irradiated with light. Then, after the bonding step of obtaining a primary laminate, and after the bonding step, the primary laminate is heated, and the adhesive layer between the first electronic component body and the second electronic component body is formed. And a heating process for obtaining an electronic component by curing the electronic component manufacturing method. It is.

  On the specific situation with the manufacturing method of the electronic component which concerns on this invention, after repeating from the said application | coating process to the said bonding process in multiple times, the said heating process is performed.

  On the specific situation with the manufacturing method of 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.

  On the specific situation with the manufacturing method of the electronic component which concerns on this invention, a said 1st electronic component main body is a semiconductor wafer, and a said 2nd electronic component main body is a cover glass.

  On the specific situation with the manufacturing method of the electronic component which concerns on this invention, in the said application | coating process, it apply | coats circulating the said inkjet light and a thermosetting adhesive.

  In a specific aspect of the method for manufacturing an electronic component according to the present invention, the inkjet device is connected to the ink tank in which the inkjet 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 part are caused to flow through the circulation flow path part and be moved to the ink tank. More, while circulating the ink jet optical and thermosetting adhesive is applied.

  On the specific situation with the manufacturing method of the electronic component which concerns on this invention, the temperature of the said inkjet light and the thermosetting adhesive which are 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.

  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.

  On the specific situation with the electronic component which concerns on this invention, a said 1st electronic component main body is a semiconductor wafer, and a said 2nd electronic component main body is a cover glass.

  The inkjet light and thermosetting adhesive according to the present invention includes a photocurable compound, a thermosetting compound, a photopolymerization initiator, and a thermosetting agent. Since the thermosetting agent represented by 1) is included, gelation can be suppressed and storage stability can be enhanced. Furthermore, when the ink for ink jet and thermosetting adhesive according to the present invention is applied using an ink jet apparatus and cured by light irradiation and then cured by heating, the adhesive is cured. The layer can be formed with high accuracy, and voids can be hardly formed in the adhesive layer.

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.

  Details of the present invention will be described below.

  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 which concerns on this invention contains the thermosetting agent represented by following formula (1) as said thermosetting agent.

  In said formula (1), R1-R15 respectively represents a hydrogen atom, an allyl group, or a C1-C18 alkyl group, and n represents the integer of 0-10.

  Since the adhesive according to the present invention has the above-described configuration, gelation can be suppressed and storage stability can be improved. Furthermore, when the adhesive according to the present invention is applied using an ink jet apparatus and cured by light irradiation and then cured by heating, the adhesive layer cured by the adhesive can be accurately and easily obtained. Can be formed. Furthermore, an adhesive layer having excellent thickness accuracy can be formed. In this invention, the thickness precision of an adhesive bond layer can be improved, the flatness of an adhesive bond layer can be improved, and the protrusion to the area | region which the adhesive bond layer does not intend can be suppressed. In addition, voids can be made difficult to occur in the adhesive layer, and high adhesion reliability can be expressed. In the present invention, peeling after moisture absorption and after a cooling cycle can be suppressed.

  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 1 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 1 rpm is 160 mPa · s or more and 1500 mPa · s or less. It is particularly preferred.

  The viscosity is measured at 25 ° C. and 1 rpm using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K2283.

  An electronic component manufacturing method according to the present invention is an application in which an adhesive layer is formed on the surface of a first electronic component body by applying the inkjet light and the thermosetting adhesive using an inkjet apparatus. A light irradiation step of irradiating the adhesive layer with light after the coating step and the coating step to advance curing of the adhesive layer; and on the adhesive layer irradiated with light after the light irradiation step. The second electronic component main body is disposed, and the first electronic component main body and the second electronic component main body are bonded together by applying pressure through the adhesive layer irradiated with light. And the said adhesive layer between the said 1st electronic component main body and the said 2nd electronic component main body is heated after the said bonding process and the bonding process which obtains a primary laminated body, and the said primary laminated body. And a heating step of obtaining an electronic component.

  Moreover, the manufacturing method of the electronic component according to the present invention includes an application step of applying an ink jet light and a thermosetting adhesive to the surface of a semiconductor wafer using an ink jet device to form an adhesive layer. The light irradiation step of forming the adhesive layer irradiated with light by causing the curing of the adhesive layer by light irradiation is opposite to the semiconductor wafer side of the adhesive layer irradiated with the light Laminating a cover glass on the surface to obtain a primary laminate, a heating step for thermosetting the adhesive layer irradiated with the light in the primary laminate, and the primary laminate after thermosetting. And a cutting step for cutting.

  If the adhesive which concerns on this invention is used, an adhesive bond layer can be formed with high precision and easily, and it can make it difficult 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 an electronic component according to the present invention. The method for manufacturing an electronic component according to the present invention is preferably a method for manufacturing a semiconductor device.

  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.

  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 contains a thermosetting agent represented by the above formula (1) as the 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 isobornyl (meth) acrylate, dihydroxycyclopentadienyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopenta Examples include nyl (meth) acrylate and naphthyl (meth) acrylate. 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-naphthyl Maleimide, N- -Xylylmaleimide, Nm-xylylmaleimide, bismaleimide methane, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, bismaleimide dodecane, N, N'-m-phenylenedimaleimide, N, N′-p-phenylene dimaleimide, 4,4′-bismaleimide diphenyl ether, 4,4′-bismaleimide diphenylmethane, 4,4′-bismaleimide-di (3-methylphenyl) methane, 4,4′-bis Maleimide-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-tolylenemaleimide, and And N, N'-m-xylylene dimaleimide and the like.

  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 adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, the photocurable compound and the photocurable compound having two or more photocurable reactive groups are: It is preferable that the photocurable compound represented by following formula (11) is included. Moreover, by using the photocurable compound represented by the following formula (11), the thickness accuracy, flatness, reduction of protrusion, and reduction of voids of the adhesive layer are further improved.

  In said formula (1), R1 and R2 represent a hydrogen atom or a methyl group, respectively.

  From the viewpoint of forming the cured adhesive layer with higher accuracy, the content of the photocurable 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. 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 100% by weight of the adhesive is 10% by weight or more, It is particularly preferable that it is 80% 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 photocuring represented by the above formula (11) in 100% by weight of the entire photocurable compound. The content of the functional compound is preferably 10% by weight or more, more preferably 30% by weight or more, further preferably 50% by weight or more, preferably 100% by weight (total amount) or less, more preferably 90% by weight or less.

  When the polyfunctional compound (A1) and the monofunctional compound (A2) are used as the photocurable compound, the compounding ratio of the polyfunctional compound (A1) and the monofunctional compound (A2) is not particularly limited. By adding the monofunctional compound (A2), the ink-jet coating is improved, but the photocurability tends to be lowered. For this reason, the content of the monofunctional compound (A2) is preferably 60 parts by weight or less, more preferably 50 parts by weight or less with respect to 100 parts by weight of the polyfunctional compound (A1).

(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 adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, the light and thermosetting compound are represented by the following formula (21). A compound is preferred.

  In said formula (21), R represents a hydrogen atom or a methyl group.

  From the viewpoint of forming the cured adhesive layer with higher accuracy, the content of the light and thermosetting compound is preferably 0.5% by weight or more, more preferably 1% in 100% by weight of the adhesive. % By weight or more, preferably 60% by weight or less, more preferably 50% 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)
The adhesive contains a thermosetting agent represented by the following formula (1) as the thermosetting agent.

  In said formula (1), R1-R15 respectively represents a hydrogen atom, an allyl group, or a C1-C18 alkyl group, and n represents the integer of 0-10. R1 to R15 may be the same or different.

  From the viewpoint of forming the adhesive layer with higher accuracy and making it more difficult to generate voids in the adhesive layer, 25 of the thermosetting agent represented by the above formula (1) measured in accordance with JIS K2283. The viscosity at 1 ° C. and 1 ° C. is preferably 1 Pa · s or more, and preferably 50 Pa · s or less. N in the formula (1) is preferably a value that satisfies the lower limit of the viscosity, and preferably a value that satisfies the upper limit of the viscosity.

  The viscosity is measured at 25 ° C. and 1 rpm using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K2283.

  Moreover, the said adhesive agent may contain the other thermosetting agent with the thermosetting agent represented by the said Formula (1).

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

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

  Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic acid, pyromellitic anhydride, Examples thereof include benzophenone tetracarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, trimellitic anhydride, and polyazeline acid anhydride. In 100% by weight of the adhesive, the total content of the thermosetting agent is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 70% by weight or less, more preferably 60% by weight or less.

  In 100% by weight of the adhesive, the content of the thermosetting agent represented by the formula (1) is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 70% by weight or less, more preferably 60%. % 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. When the adhesive contains a solvent, the content of the solvent is 1% by weight or less in 100% by weight of the adhesive. 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 is preferably 1% by weight or less in 100% by weight of the adhesive.

(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 1% by weight or less, more preferably 0.5% by weight or less, and still more preferably 0.3% by weight. % Or less.

(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, 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 cross-sectional view 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 a semiconductor element.

  Examples of the support member for mounting the semiconductor element include a circuit board and a lead frame.

  Since an adhesive layer formed with high accuracy is particularly required, the electronic component body is preferably a support member on which a semiconductor element is mounted, 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 a semiconductor element, such as a circuit board, a lead frame, or a semiconductor element. More preferably. Since the adhesive layer formed with high accuracy is particularly required, the second electronic component body is preferably a semiconductor element.

  It is also preferable that the first electronic component main body is a semiconductor wafer and the second electronic component main body is a cover glass.

  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 section, it is preferable that the pressure is maintained at an appropriate pressure and that 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. 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.

  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). , Bonding process). 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 main body 2 and the second electronic component main body 4 are bonded together by applying pressure through the adhesive layer 12A irradiated with light to obtain the primary laminated body 1A (lamination process, bonding) Joint process).

  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. You may perform the said heating process, after repeating from the said application | coating process to the said lamination process in multiple times.

  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 increasing the adhesive discharge property and forming the cured adhesive layer with higher accuracy, the viscosity at the time of discharging the adhesive is 3 mPa · s or more, more preferably 5 mPa · s or more, and still more preferably. 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 for voids to be generated in the adhesive layer, the viscosity at 25 ° C. at the time of discharging the adhesive 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.

  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 divided semiconductor wafer (semiconductor element) 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 divided 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 divided 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 stacked structure 52 includes a substrate 53, an adhesive layer 54, and a second divided semiconductor wafer (semiconductor element) 55 stacked on the substrate 53 via the adhesive layer 54. A second divided semiconductor wafer 55 is disposed on the substrate 53. On the substrate 53, the second divided semiconductor wafer 55 is indirectly laminated. In plan view, the substrate 53 is larger than the second divided semiconductor wafer 55. 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 divided 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 divided semiconductor wafer 55. The other end of the wiring 56 is connected to a first connection terminal 53 a provided on the substrate 53. The connection terminal 55 a and the first connection terminal 53 a are electrically connected by the wiring 56. 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 divided semiconductor wafer (semiconductor element) 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, an adhesive layer 61 is formed on the second divided semiconductor wafer 55 by discharging a photo-curing and thermo-curing and liquid adhesive from the ink jet device. Can be obtained at 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)
Photocurable compound: 30 parts by weight of tricyclodecane dimethanol diacrylate (“IRR-214K” manufactured by Daicel Ornex Co., Ltd.), 10 parts by weight of isobornyl acrylate (“IBOA” manufactured by Kyoeisha Chemical Co., Ltd.), and photopolymerization started Agent: 4.5 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (“IRGACURE 369” manufactured by BASF) and thermosetting compound: bisphenol A type epoxy resin ( DIC "EXA850CRP") 20 parts by weight, thermosetting agent: liquid phenolic resin (Maywa Kasei "MEH8000H") 30 parts by weight, light and thermosetting compound: glycidyl methacrylate (NOF "Blemmer GH" )) 10 parts by weight and curing accelerator: DBU-octylate ("UCAT SA" manufactured by San Apro) 102 ") 0.5 part by weight was mixed to obtain a curable composition for inkjet.

(Examples 2 to 13 and Comparative Examples 1 and 2)
A curable adhesive for inkjet was obtained in the same manner as in Example 1 except that the components shown in Table 1 below were changed as shown in Table 2 below.

(Evaluation)
(1) Viscosity Based on JIS K2283, the viscosity η1 at 25 ° C. and 1 rpm of the adhesive immediately after production was measured using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.). The viscosity η1 of the adhesive was determined 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 viscosity is more than 1600 mPa · s

(2) Confirmation of semiconductor device voids FR4 glass epoxy substrate (thickness 0.3 mm, commercially available solder resist coated, 10 mm long x 10 mm wide semiconductor chips are placed in 3 rows by 9 columns in 27 rows 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. A 30 μm adhesive layer 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 stacking the silicon bare chips, 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 of 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)

(3) Confirmation of protruding adhesive layer of semiconductor device Using an optical microscope ("Digital Microscope VH-Z100" manufactured by Keyence Corporation), protruding adhesive layer of the semiconductor device obtained by the evaluation in (2) above Were observed and evaluated according to the following criteria.

[Extrusion criteria]
OO: 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: Protrusion was observed (protrusion distance of 200 μm or more)

(4) Storage stability (pot life length)
After the adhesive was circulated in the ink jet apparatus at 70 ° C. for 8 hours, it was confirmed whether or not the adhesive could be discharged from the ink jet head.

[Criteria for storage stability]
○: Adhesive could be ejected from the inkjet head ×: Adhesive was cured before ejection, or the viscosity of the adhesive was increased, and the adhesive could not be ejected from the inkjet head

(5) Hygroscopic reflow test of semiconductor device The semiconductor devices (27 pieces) obtained in the evaluation of (2) above were allowed to stand for 168 hours at 85 ° C. and 85 RH% to absorb moisture, and then solder reflow oven (preheat 150 ° C. × 100 seconds, reflow [maximum temperature 260 ° C.] 1 cycle and 3 cycles of the semiconductor device, 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. The moisture absorption reflow test was evaluated according to the following criteria.

[Criteria for moisture absorption reflow test]
○○: No peeled semiconductor device ○: One or more peeled semiconductor devices (less than 3)
×: Three or more peeled semiconductor devices (problems in use)

(6) Semiconductor device cooling cycle test (adhesion reliability / long-term reliability: cooling cycle evaluation)
About the obtained semiconductor device, after hold | maintaining for 10 minutes at -55 degreeC using a liquid tank type thermal shock tester ("TSB-51" by ESPEC), it heated up to 150 degreeC and was 10 minutes at 150 degreeC. A cold cycle test was conducted in which the temperature lowering to −50 ° C. was held as one cycle. The semiconductor device was taken out after 250 cycles and 500 cycles, and the peeling of the adhesive layer of the semiconductor device was observed using an ultrasonic exploration imaging device (“mi-scope hyper II” manufactured by Hitachi Construction Machinery Finetech Co., Ltd.). The thermal cycle test was evaluated according to the following criteria.

[Criteria for cooling cycle test]
○○: 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 ... Substrate 53a ... 1st connection terminal 53b ... 2nd connection terminal 54, 61, 72 ... Adhesive layer 55 ... 2nd divided semiconductor wafer ( Semiconductor element)
55a, 73a ... connection terminal 56, 63, 74 ... wiring 62, 73 ... first divided semiconductor wafer (semiconductor element)
62a ... Connection terminal

Claims (18)

An adhesive used by being applied using an ink jet device and cured by heating after being cured by light irradiation,
Including a photocurable compound, a thermosetting compound, a photopolymerization initiator, and a thermosetting agent,
The inkjet light and thermosetting adhesive containing the thermosetting agent represented by following formula (1) as said thermosetting agent.

In said formula (1), R1-R15 respectively represents a hydrogen atom, an allyl group, or a C1-C18 alkyl group, and n represents the integer of 0-10.   The inkjet light according to claim 1, wherein the thermosetting agent represented by the formula (1) measured in accordance with JIS K2283 has a viscosity of 1 Pa · s to 50 Pa · s at 25 ° C. at 1 rpm. And thermosetting adhesives.   The inkjet light and thermosetting adhesive according to claim 1 or 2, wherein the viscosity at 1 rpm at 25 ° C measured in accordance with JIS K2283 is 160 mPa · s or more and 1600 mPa · s or less. The light for inkjets and thermosetting adhesive of any one of Claims 1-3 in which the said photocurable compound contains the photocurable compound represented by following formula (11).

In the formula (11), R1 and R2 each represent a hydrogen atom or a methyl group.   The inkjet light and thermosetting adhesive according to claim 1, comprising light and a thermosetting compound. The light and thermosetting adhesive for inkjet according to claim 5, wherein the light and thermosetting compound are a light and thermosetting compound represented by the following formula (21).

In said formula (21), R represents a hydrogen atom or a methyl group. Contains or does not contain solvent,
The inkjet light and thermosetting adhesive according to any one of claims 1 to 6, wherein when the adhesive contains the solvent, the content of the solvent is 1% by weight or less. Does not contain filler or contains
When the adhesive contains the filler, the inkjet light and thermosetting adhesive according to any one of claims 1 to 7, wherein the filler content is 1% by weight or less. On the surface of a 1st electronic component main body, the inkjet light and thermosetting adhesive of any one of Claims 1-8 are apply | coated using an inkjet apparatus, and an adhesive bond layer is formed. Application process;
After the application step, the light irradiation step of irradiating the adhesive layer with light to advance the curing of the adhesive layer;
After the light irradiation step, a second electronic component main body is disposed on the adhesive layer irradiated with light, and the first electronic component main body and the second electronic component main body are irradiated with light. A bonding step of applying a pressure and bonding together through the adhesive layer thus obtained to obtain a primary laminate;
After the bonding step, heating the primary laminate, curing the adhesive layer between the first electronic component body and the second electronic component body, and obtaining an electronic component; An electronic component manufacturing method comprising:   The manufacturing method of the electronic component of Claim 9 which performs the said heating process, after repeating from the said application | coating process to the said bonding process in multiple times. The first electronic component main body is a supporting member or a semiconductor element for mounting a semiconductor element;
The method of manufacturing an electronic component according to claim 9 or 10, wherein the second electronic component main body is a semiconductor element. The first electronic component body is a semiconductor wafer;
The manufacturing method of the electronic component of Claim 9 or 10 whose said 2nd electronic component main body is a cover glass.   The manufacturing method of the electronic component in any one of Claims 9-12 which apply | coats in the said application | coating process, circulating the said inkjet light and a thermosetting adhesive. 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. 14. The electronic component manufacturing method according to claim 13, wherein the adhesive light is applied while circulating the light for the inkjet and the thermosetting adhesive by moving the adhesive in the circulation flow path portion and moving to the ink tank. Method.   The method of manufacturing an electronic component according to claim 13 or 14, wherein the temperature of the inkjet light and the thermosetting adhesive being circulated is 40 ° C or higher and 100 ° C or lower. A first electronic component body, a second electronic component body, and an adhesive layer connecting the first electronic component body and the second electronic component body,
Heating after the adhesive layer is applied with the inkjet light and thermosetting adhesive according to any one of claims 1 to 8 using an inkjet apparatus, and is cured by light irradiation. An electronic component formed by curing with 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 16, wherein the second electronic component main body is a semiconductor element. The first electronic component body is a semiconductor wafer;
The electronic component according to claim 16, wherein the second electronic component main body is a cover glass.

Images