JPWO2012017955A1 - Manufacturing method of semiconductor wafer with adhesive layer, photosensitive adhesive, and semiconductor device - Google Patents

Abstract

A step of applying a photosensitive adhesive to the entire surface of one of the semiconductor wafers by a screen printing method to form a photosensitive adhesive layer; and a step of forming the photosensitive adhesive layer into a B-stage by exposure. The manufacturing method of the semiconductor wafer with an adhesive bond layer.

Description

  The present invention relates to a method for manufacturing a semiconductor wafer with an adhesive layer, a photosensitive adhesive, and a semiconductor device. More specifically, a photosensitive adhesive for die bonding used as a bonding material (die bonding material) when laminating semiconductor elements such as IC and LSI and a support member such as a lead frame or an insulating support substrate, or semiconductor chips. The present invention relates to a semiconductor wafer manufacturing method and a semiconductor device using the same.

  As a bonding material between a semiconductor element such as IC or LSI and a support member, or a bonding material when laminating semiconductor chips, an adhesive film using a specific polyimide resin, a conductive filler or an inorganic filler on a specific polyimide resin Added die bonding adhesive films are known.

  In recent years, it has been studied to improve the efficiency of the assembly process of semiconductor devices by performing them collectively on a semiconductor wafer (hereinafter sometimes simply referred to as “wafer”). In addition, as the semiconductor chips are stacked, the thickness of the wafer tends to be reduced. In general, a process using an adhesive film or a process of applying a die bonding adhesive to a semiconductor wafer by a spin coating method is applied.

  As a process using an adhesive film, an adhesive film is laminated on the entire surface of a semiconductor wafer, a support film for dicing is further laminated, and a semiconductor chip on which the adhesive film is laminated is separated into a semiconductor substrate or a semiconductor chip by a dicing process. The method of sticking to is mentioned.

  As a method for applying an adhesive to the entire surface of a semiconductor wafer, a spin coating method in which a liquid adhesive on a semiconductor wafer is applied to the entire surface by high-speed rotation is also widely known.

  In the process of using a thin film wafer, the strength of the wafer tends to decrease. Therefore, after the wafer back grinding step, it is desirable to apply a die bonding adhesive while the back grind tape is bonded to form a B stage.

JP 2008-98213 A Japanese Patent Publication No. 5-54262

  However, when an adhesive film is used, the adhesive film is likely to be wasted at portions other than the wafer in the process of laminating the adhesive film on the wafer. Even in the case of using the spin coating method, it is necessary to supply and discard the adhesive on the semiconductor wafer until a uniform adhesive layer is formed, and the adhesive is likely to be wasted.

  Furthermore, the heat resistance of the back grind tape is about 80 ° C. to 100 ° C., and the back grind tape contracts by heating at 100 ° C. or higher. Shrinkage of the back grind tape can cause warping of the semiconductor wafer. Even when heating at 80 ° C. or lower, the semiconductor wafer tends to warp during cooling after heating due to the difference between the thermal expansion coefficient of the back grind tape and the thermal expansion coefficient of the semiconductor wafer.

  The present invention has been made in view of the above circumstances, and is capable of forming an adhesive layer on a semiconductor wafer with a uniform film thickness and less waste of the adhesive, and for the B-stage of the adhesive layer. The manufacturing method of the semiconductor wafer with an adhesive layer which can avoid the curvature of the semiconductor wafer resulting from heating, the photosensitive adhesive used for the manufacturing method, and the semiconductor wafer with an adhesive layer which can be manufactured by the manufacturing method An object of the present invention is to provide a semiconductor device and a photosensitive adhesive for screen printing.

  The present invention includes a step of applying a photosensitive adhesive to a whole surface of a semiconductor wafer by a screen printing method to form a photosensitive adhesive layer, and a step of exposing the photosensitive adhesive layer to a B-stage by exposure. A method for manufacturing a semiconductor wafer with an adhesive layer is provided.

  According to the manufacturing method of the present invention, an adhesive layer can be formed on a semiconductor wafer with a uniform film thickness and less waste of the adhesive, and also due to heating for B-stage formation of the adhesive layer. Semiconductor wafer warpage can be avoided.

  The photosensitive adhesive can contain a thermosetting resin, a radiation polymerizable compound, and a photopolymerization initiator.

  The photosensitive adhesive can further contain a thermosetting initiator.

  The photosensitive adhesive may have a viscosity at 25 ° C. of 1 to 100 Pa · s, and the photosensitive adhesive may have a thixotropy index of 1.0 to 3.0.

  The photosensitive adhesive which concerns on this invention contains a thermosetting resin, a radiation polymerizable compound, and a photoinitiator, and is used in order to form a photosensitive adhesive layer in the said manufacturing method.

  The present invention also provides a process of obtaining a semiconductor chip with an adhesive layer by separating the semiconductor wafer with an adhesive layer obtained by the manufacturing method according to the present invention, and supporting the semiconductor chip of the semiconductor wafer with an adhesive layer. And a step of adhering to a member or another semiconductor chip.

  Furthermore, the present invention contains a thermosetting resin, a radiation polymerizable compound and a photopolymerization initiator, has a viscosity at 25 ° C. of 1 to 100 Pa · s, and a thixotropic index of 1.0 to 3.0. A photosensitive adhesive for screen printing is provided.

  According to the present invention, an adhesive layer can be formed on a semiconductor wafer with a uniform film thickness and less waste of the adhesive, and the warp of the semiconductor wafer due to heating for B-stage of the adhesive layer is caused. Provided are a method for manufacturing a semiconductor wafer with an adhesive layer, a photosensitive adhesive used in the manufacturing method, a semiconductor device including the semiconductor wafer that can be manufactured by the manufacturing method, and a photosensitive adhesive for screen printing. The

It is a schematic diagram which shows one Embodiment of the manufacturing method of a semiconductor device. It is a schematic diagram which shows one Embodiment of the manufacturing method of a semiconductor device. It is a schematic diagram which shows one Embodiment of the manufacturing method of a semiconductor device. It is a schematic diagram which shows one Embodiment of the manufacturing method of a semiconductor device. It is a schematic diagram which shows one Embodiment of the manufacturing method of a semiconductor device. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device.

  DESCRIPTION OF EMBODIMENTS Hereinafter, preferred embodiments of a method for producing a semiconductor wafer with an adhesive layer, a photosensitive adhesive, a semiconductor device, and a photosensitive adhesive for screen printing according to the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments.

  The method for manufacturing a semiconductor device according to the present embodiment includes a step of applying a photosensitive adhesive to a whole surface of a semiconductor wafer by a screen printing method to form a photosensitive adhesive layer (photosensitive adhesive layer forming step). ), And a step of B-stage the photosensitive adhesive layer by exposure (B-stage forming step), and a step of cutting the semiconductor wafer together with the B-staged photosensitive adhesive layer (dicing step).

(Photosensitive adhesive layer forming process)
A semiconductor wafer 6 shown in FIG. 1 is used to form semiconductor chips 13a and 13b (FIG. 6) incorporated in a semiconductor package (semiconductor device) (FIG. 6). The semiconductor wafer 6 is typically a silicon wafer. A circuit may already be formed in the semiconductor wafer 6 by a previous process. In the photosensitive adhesive layer forming step, for example, as shown in FIG. 1, the photosensitive adhesive 5 is applied to the surface (back surface) opposite to the surface on which the circuit of the semiconductor wafer 6 is formed by screen printing. Apply (print). As a result, a photosensitive adhesive layer 7 having a uniform thickness is formed on the back surface of the semiconductor wafer 6 as shown in FIG.

  The screen printing method generally includes the following two methods. One is a method using a so-called metal printing plate in which a patterned opening is provided on a flat metal plate. In this construction method, a metal printing plate is placed on an object to be printed, and ink is applied by sweeping ink mounted on the metal printing plate with a metal plate called a squeegee. By this step, the ink is applied in the shape of the opening pattern provided on the metal printing plate.

  As another screen printing method, there is a method using a so-called mesh printing plate in which a mesh prepared by knitting a thread of stainless steel, nylon, polyester or the like is filled with a resin or the like while leaving only a portion to be applied. In this method, ink mounted on a mesh printing plate is swept with a resin or metal plate called a scraper. By this step, the ink penetrates into the opening not filled with the resin or the like of the mesh printing plate. Next, the mesh printing plate is swept using a squeegee made of polyurethane or silicon rubber. By this step, the ink that has permeated the opening is transferred onto the printing target, and the printing step is completed.

  In this embodiment, in any printing method, the adhesive can be selectively applied only to a desired position and region, so that waste of the adhesive can be reduced and the material yield is excellent.

  When printing is performed in a relatively wide range by a construction method using a metal printing plate, there is no member in the opening, so that no stress is generated from the printing plate against the pressure of the squeegee in the opening. For this reason, the pressure is concentrated at the center of the squeegee, the central portion of the squeegee is strongly pushed into the opening, and the film thickness of the photosensitive adhesive layer tends to decrease at the center of the opening. That is, generally, the wider the opening, the stronger the central portion of the squeegee is pushed, and the thickness of the photosensitive adhesive layer at the center tends to decrease.

  On the other hand, in the construction method using the mesh printing plate, since the mesh thread is also present in the opening, stress from the mesh printing plate with respect to the pressure of the squeegee is generated. That is, the mesh yarn in the opening also functions as a support member even at the center of the squeegee, so that the squeegee is not strongly pushed into the opening. For this reason, the film thickness does not decrease even in the center of the squeegee, and a uniform photosensitive adhesive layer can be obtained.

  In the screen printing method in the present embodiment, a method using a mesh printing plate is preferable from the viewpoint of providing a photosensitive adhesive layer having a uniform film thickness over a relatively wide range of the entire wafer surface.

(B-stage process)
The photosensitive adhesive layer 7 is a photosensitive adhesive layer having adhesion to an adherend after being B-staged by exposure. The applied photosensitive adhesive layer 7 is irradiated with visible light or ultraviolet rays by an exposure device, and the photosensitive adhesive 5 constituting the photosensitive adhesive layer 7 is made into a B-stage. As a result, a polymerization reaction by the photopolymerization initiator and the radiation polymerizable compound contained in the photosensitive adhesive 5 proceeds, and the B-staged photosensitive adhesive layer 8 has appropriate tackiness and adhesiveness. Specifically, the photosensitive adhesive layer 8 is fixed to the semiconductor wafer 6. In this way, the photosensitive adhesive layer 7 is B-staged not by heating but by exposure, so that the photosensitive adhesive 5 can be applied and photosensitive while the back grind tape is still bonded to the semiconductor wafer 6. The adhesive adhesive layer 7 can be made into a B-stage.

  The exposure is preferably performed under a nitrogen atmosphere or under a vacuum condition, or in a state where a transparent cover film is laminated on the photosensitive adhesive layer 7 from the viewpoint of avoiding the inhibition of the photopolymerization reaction due to oxygen. More specifically, the photosensitive adhesive layer 8 that has been B-staged by exposure is divided into individual pieces by dicing, and appropriate adhesiveness that enables peeling from the support during dicing, and a semiconductor chip and It has adhesiveness to an adherend such as a glass substrate. Details of the photosensitive adhesive layer 8 having such a function will be described later.

When the surface tack force (surface tack force) at 30 ° C. of the exposed photosensitive adhesive layer 8 is 200 gf / cm ² or less, it can be confirmed that the photosensitive adhesive layer 8 is B-staged. .

When the surface tack force at 30 ° C. exceeds 200 gf / cm ² , the adhesiveness of the surface of the photosensitive adhesive layer 8 at room temperature increases, and the handleability tends to decrease. Furthermore, the peelability from the dicing film after dicing tends to decrease, and the pick-up property tends to decrease. Further, when the surface tack force at 30 ° C. is 1 gf / cm ² or less, the tackiness of the photosensitive adhesive is lowered, and water penetrates into the interface between the photosensitive adhesive and the dicing film during dicing, and the chip jumps. Tend to occur.

It is preferable that the surface tack force at 120 ° C. of the exposed photosensitive adhesive layer 8 is 200 gf / cm ² or more. When the surface tack force at 120 ° C. is less than 200 gf / cm ² , the thermocompression bonding property is impaired, voids are generated during thermocompression bonding, and the thermocompression bonding temperature tends to increase. Moreover, when the surface tack force at 120 ° C. is 500 gf / cm ² or more, the photosensitive adhesive excessively spreads during thermocompression bonding, and the photosensitive adhesive tends to protrude from the side surface of the chip.

The surface tack force is a value measured as follows. A photosensitive adhesive is applied onto a silicon wafer by screen printing, and the resulting coating film is subjected to nitrogen by a high-precision parallel exposure machine (“EXM-1172-B-∞” (trade name), manufactured by Oak Seisakusho). Exposure is performed at 1000 mJ / cm ² in an atmosphere. Then, using a probe tacking tester manufactured by Reska, 30 ° C. and 120 ° C. under conditions of probe diameter: 5.1 mm, peeling speed: 10 mm / s, contact load: 100 gf / cm ² , contact time: 1 s. The tack force on the surface of the photosensitive adhesive layer 8 is measured. Instead of the above high-accuracy parallel exposure machine, a parallel exposure machine (manufactured by Luminous Co., Ltd., “ML-210FM mask aligner” (trade name)) may be used.

(Dicing process)
Next, the semiconductor wafer 20 with the adhesive layer having the photosensitive adhesive layer 8 formed on the semiconductor wafer 6 and the back surface thereof is diced from the wafer side, and the separated semiconductor chip 11 is manufactured (FIG. 4). ). That is, the semiconductor wafer 6 is cut into a plurality of semiconductor chips 11 by cutting the semiconductor wafer 6 with a dicing machine. Prior to this dicing step, it is preferable that the dicing film 10 is attached to the back surface of the semiconductor wafer 6 on which the photosensitive adhesive layer 8 is formed. Affixing may be performed while heating if necessary. For example, it is preferably carried out using a dicing blade 12 with the dicing film 10 fixed to the frame (wafer ring) 9 (FIG. 3) (FIG. 4). The separated semiconductor chip 11 with the photosensitive adhesive layer is picked up using a die bonding apparatus or the like (FIG. 5).

  As shown in FIG. 6, the semiconductor chip 13a obtained by the dicing process is placed on a support member 14 prepared separately. Alternatively, a semiconductor chip 13 b different from the semiconductor chip 13 a is disposed on the semiconductor chip 13 a that is bonded to the support member 14 in advance. At this time, the photosensitive adhesive layers 16 and 17 are thermocompression bonded to bond the semiconductor chip 13a and the support member 14, and the semiconductor chip 13b and the semiconductor chip 13a, and the semiconductor chips 13a and 13b are connected to the support member 14 or the semiconductor. It is bonded and fixed to the chip 13a.

  After that, the bonding pads on the semiconductor chips 13a and 13b and the support member 14 are connected by the bonding wires 18, and the semiconductor chips 13a and 13b are sealed together with the bonding wires 18 by the sealing material 15 to be shown in FIG. Such a semiconductor package (semiconductor device) is completed.

  According to the semiconductor device manufacturing method described above, the photosensitive adhesive 5 for bonding the semiconductor chip 13a and the support member 14 or the semiconductor chips 13a and 13b is applied only on the semiconductor wafer 6 by screen printing. Is possible. Thereby, it is possible to apply a desired film thickness by changing the printing plate regardless of the composition of the photosensitive adhesive 5. Accordingly, it is possible to reduce the waste of the adhesive in the manufacturing method of the semiconductor device or the semiconductor wafer with the adhesive layer, and to apply a plurality of film thicknesses with a single adhesive.

  Next, a preferred embodiment of the photosensitive adhesive according to this embodiment will be described. This photosensitive adhesive can be suitably used as the photosensitive adhesive 5 in the semiconductor device manufacturing method described above.

  The photosensitive adhesive according to the present embodiment contains (A) a thermosetting resin, (B) a radiation polymerizable compound, and (C) a photopolymerization initiator.

  (A) The thermosetting resin is not particularly limited as long as it is a component composed of a reactive compound that causes a crosslinking reaction by heating. For example, epoxy resin, cyanate ester resin, maleimide resin, allyl nadiimide resin, phenol Resin, urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, resorcinol formaldehyde resin, xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate Resin, resin containing tris (2-hydroxyethyl) isocyanurate, resin containing triallyl trimellitate, thermosetting resin synthesized from cyclopentadiene, and thermosetting by trimerization of aromatic dicyanamide Sex tree And the like. Of these, epoxy resins, maleimide resins, and allyl nadiimide resins are preferred in that they can have excellent adhesive strength at high temperatures in combination with polyimide resins. In addition, these thermosetting resins can be used individually by 1 type or in combination of 2 or more types.

  As an epoxy resin, what contains at least 2 or more epoxy group in a molecule | numerator is preferable, and the point of the thermocompression bonding property, sclerosis | hardenability, and hardened | cured material property to a glycidyl ether type epoxy resin of phenol is more preferable. Examples of such resins include bisphenol A type (or AD type, S type, and F type) glycidyl ether, water-added bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, and propylene oxide adduct. Bisphenol A type glycidyl ether, phenol novolac resin glycidyl ether, cresol novolac resin glycidyl ether, bisphenol A novolac resin glycidyl ether, naphthalene resin glycidyl ether, trifunctional (or tetrafunctional) glycidyl ether, dicyclo Examples include glycidyl ether of pentadiene phenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) glycidylamine, and glycidylamine of naphthalene resin. It is. These can be used individually by 1 type or in combination of 2 or more types.

  As the epoxy resin, it is possible to use a high-purity product in which the impurity ions, alkali metal ions, alkaline earth metal ions, halogen ions, particularly chlorine ions and hydrolyzable chlorine are reduced to 300 ppm or less, to prevent electromigration. This is preferable from the viewpoint of preventing corrosion of the metal conductor circuit.

  The amount of the thermosetting resin such as an epoxy resin is preferably 10 to 80% by mass with respect to the total amount of the photosensitive adhesive, and 20 to 60% by mass from the viewpoint of the reliability of the photosensitive adhesive. More preferred. When this amount exceeds 80% by mass, the viscosity of the photosensitive adhesive tends to increase, and the printability tends to decrease. On the other hand, when it is less than 10% by mass, there is a tendency that sufficient thermocompression bonding property and high temperature adhesiveness cannot be obtained. The upper limit and lower limit of the amount of the thermosetting resin are 10% by mass, 20% by mass, 33% by mass, 42.5% by mass, 60% by mass, or 80% by mass with respect to the total amount of the photosensitive adhesive. Also good.

  (A) The thermosetting resin preferably has a 5% mass reduction temperature of 150 ° C. or higher, more preferably 180 ° C. or higher, and even more preferably 200 ° C. or higher. Here, the 5% mass reduction temperature refers to a thermosetting resin using a differential thermothermal gravimetric simultaneous measurement apparatus (manufactured by SII Nanotechnology: TG / DTA6300), a heating rate of 10 ° C./min, and a nitrogen flow (400 ml). / Min) is a 5% mass loss temperature when measured under. By applying a thermosetting resin having a high 5% mass reduction temperature, volatilization of the thermosetting resin during thermocompression bonding or thermosetting can be suppressed. Examples of such thermosetting resins having heat resistance include epoxy resins having an aromatic ring in the molecule, and in particular, trifunctional (or tetrafunctional) glycidylamine and bisphenol from the viewpoint of adhesion and heat resistance. A-type (or AD-type, S-type, F-type) glycidyl ether is preferably used.

  The photosensitive adhesive according to this embodiment preferably contains a thermosetting initiator (curing accelerator). The thermosetting initiator is not particularly limited as long as it is a compound that accelerates curing or polymerization of the epoxy resin by heating, and examples thereof include phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatics. Acid anhydride, alicyclic acid anhydride, aromatic acid anhydride, dicyandiamide, organic acid dihydrazide, boron trifluoride amine complex, imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate 2-ethyl-4-methylimidazole-tetraphenylborate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, 2- (0- [1 ′ methylpropylideneamino] carboxyamino) ethyl methacrylate 1,8-dia Bicyclo [5,4,0] undecene-7-tetraphenylborate and tertiary amines. Among these, imidazoles are preferably used from the viewpoint of solubility and dispersibility when no solvent is contained. As for the quantity of a thermosetting initiator, 0.01-50 mass parts is preferable with respect to 100 mass parts of thermosetting resins, such as an epoxy resin. Also, imidazoles are particularly preferable from the viewpoints of adhesiveness, heat resistance, and storage stability. The upper limit and lower limit of the amount of the thermosetting initiator may be 0.01 parts by mass, 0.67 parts by mass, 1 part by mass or 50 parts by mass with respect to 100 parts by mass of the thermosetting resin.

  As imidazoles, the reaction start temperature is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, and most preferably 100 ° C. or higher. When the reaction start temperature is less than 50 ° C., the storage stability of the photosensitive adhesive is lowered, so that the viscosity of the photosensitive adhesive is increased and the film thickness tends to be difficult to control.

  As the imidazoles, it is preferable to use a compound having an average particle size of 10 μm or less, more preferably 8 μm or less, and most preferably 5 μm or less. By using imidazoles having such an average particle diameter, the change in the viscosity of the photosensitive adhesive can be suppressed, and the precipitation of imidazoles can be suppressed. In addition, when a thin film of photosensitive adhesive is formed, a uniform film can be obtained by reducing surface irregularities. Further, it is considered that the outgas can be reduced because the curing of the photosensitive adhesive can be uniformly progressed during the curing. Moreover, favorable storage stability can be obtained by using imidazole with poor solubility in an epoxy resin.

  As imidazoles, imidazoles that are soluble in epoxy resins can also be used. By using such imidazoles, surface irregularities when a thin film of a photosensitive adhesive is formed can be further reduced. Such imidazoles include, but are not limited to, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Examples include phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole and the like.

  The photosensitive adhesive may contain a phenol compound as a curing agent. As the phenolic compound, a phenolic compound having at least two phenolic hydroxyl groups in the molecule is more preferable. Examples of such compounds include phenol novolak, cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol novolak, dicyclopentadiene phenol novolak, xylylene-modified phenol novolak, naphthol-based compound, trisphenol-based compound, tetrakisphenol novolak, Bisphenol A novolac, poly-p-vinylphenol and phenol aralkyl resins are mentioned. Among these, those having a number average molecular weight in the range of 400 to 4000 are preferable. Accordingly, it is possible to suppress outgassing during heating that causes contamination of the semiconductor element or the device during heating in assembling the semiconductor device. The amount of the phenolic compound is preferably 50 to 120 parts by mass and more preferably 70 to 100 parts by mass with respect to 100 parts by mass of the thermosetting resin.

  (B) Examples of the radiation polymerizable compound include compounds having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, and a maleimide. Group, nadiimide group, (meth) acryl group and the like. From the viewpoint of reactivity, a (meth) acryl group is preferable, and a monofunctional (meth) acrylate is preferably included. By adding monofunctional (meth) acrylate, it is possible to reduce the crosslink density of the photosensitive adhesive, especially during exposure for B-stage, and the post-exposure thermocompression, low stress and adhesiveness can be reduced. It can be in a good state.

  The 5% mass reduction temperature of the monofunctional (meth) acrylate is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 150 ° C. or higher, and 180 ° C. or higher. Is most preferred. Here, the 5% mass reduction temperature means a monofunctional (meth) acrylate using a differential thermothermal gravimetric simultaneous measurement apparatus (manufactured by SII Nanotechnology: TG / DTA6300), a heating rate of 10 ° C./min, and a nitrogen flow. 5% mass loss temperature when measured under (400 ml / min). By applying a monofunctional (meth) acrylate having a high 5% mass reduction temperature, it is possible to suppress volatilization of unreacted monofunctional (meth) acrylate remaining after B-staging by exposure during thermocompression bonding or thermosetting. .

  If it is such a monofunctional (meth) acrylate, there is no particular limitation, but glycidyl group-containing (meth) acrylate, phenol EO modified (meth) acrylate, phenol PO modified (meth) acrylate, nonylphenol EO modified (meth) acrylate , Aromatic (meth) acrylates such as nonylphenol PO-modified (meth) acrylate, phenolic hydroxyl group-containing (meth) acrylate, hydroxyl group-containing (meth) acrylate, phenylphenol glycidyl ether (meth) acrylate, and phenoxyethyl (meth) acrylate , Imide group-containing (meth) acrylate, carboxyl group-containing (meth) acrylate, isoboronyl-containing (meth) acrylate, dicyclopentadienyl group-containing (meth) acrylate, and isoboronyl Meth) acrylate can be used.

  The monofunctional (meth) acrylate preferably has a urethane group, an isocyanuric group, an imide group, or a hydroxyl group from the viewpoints of adhesion to an adherend after B-stage formation, adhesion after curing, and heat resistance, In particular, a monofunctional (meth) acrylate having an imide group in the molecule is preferable.

  A monofunctional (meth) acrylate having an epoxy group can also be preferably used. The monofunctional (meth) acrylate having an epoxy group preferably has a 5% mass reduction temperature of 150 ° C. or more from the viewpoints of storage stability, adhesiveness, low outgas properties, heat resistance reliability, and moisture resistance reliability. The temperature is more preferably 180 ° C. or higher, and most preferably 200 ° C. or higher. Although it does not specifically limit as such a monofunctional (meth) acrylate which has an epoxy group, The said heat resistance can be satisfied by using the polyfunctional epoxy resin whose 5% mass reduction | decrease temperature is 150 degreeC or more as a raw material. .

  Although it does not specifically limit as monofunctional (meth) acrylate which has an epoxy group, The functional group which reacts with an epoxy group other than glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl methacrylate glycidyl ether And compounds obtained by reacting a compound having an ethylenically unsaturated group with a polyfunctional epoxy resin. Although it does not specifically limit as a functional group which reacts with the said epoxy group, An isocyanate group, a carboxyl group, a phenolic hydroxyl group, a hydroxyl group, an acid anhydride, an amino group, a thiol group, an amide group etc. are mentioned. These compounds can be used individually by 1 type or in combination of 2 or more types.

  The monofunctional (meth) acrylate having an epoxy group is, for example, in the presence of triphenylphosphine or tetrabutylammonium bromide, a polyfunctional epoxy resin having at least two epoxy groups in one molecule, and 1 equivalent of an epoxy group. On the other hand, it is obtained by reacting 0.1 to 0.9 equivalent of (meth) acrylic acid. Also, by reacting a polyfunctional isocyanate compound with a hydroxy group-containing (meth) acrylate and a hydroxy group-containing epoxy compound in the presence of dibutyltin dilaurate, or reacting a polyfunctional epoxy resin with an isocyanate group-containing (meth) acrylate. And glycidyl group-containing urethane (meth) acrylate and the like.

  The monofunctional (meth) acrylate having an epoxy group is 5% by mass from the viewpoint of storage stability, adhesiveness, low outgassing of the package during assembly heating of the semiconductor device and after assembly of the semiconductor device, heat resistance and moisture resistance. The decrease temperature is preferably 150 ° C. or higher in that it can suppress volatilization due to heat drying or segregation on the surface during the formation of an adhesive film (photosensitive adhesive layer), and voids, separation or adhesion due to outgassing during thermosetting. It is more preferably 180 ° C. or higher in terms of being able to suppress deterioration in properties, and even more preferably 200 ° C. or higher, and 260 ° C. in terms of being able to suppress voids and peeling due to volatilization of unreacted components during reflow. The above is most preferable. As such a monofunctional (meth) acrylate having an epoxy group, a compound having an aromatic ring in the molecule is preferable.

  Furthermore, the monofunctional (meth) acrylate having an epoxy group has a high purity in which impurity ions such as alkali metal ions, alkaline earth metal ions, halogen ions, especially chlorine ions and hydrolyzable chlorine are reduced to 1000 ppm or less. It is preferable to use a product from the viewpoint of preventing electromigration and preventing corrosion of a metal conductor circuit. For example, the impurity ion concentration can be satisfied by using a polyfunctional epoxy resin with reduced alkali metal ions, alkaline earth metal ions, halogen ions, and the like as a raw material. The total chlorine content can be measured according to JIS K7243-3.

  The monofunctional (meth) acrylate component having an epoxy group that satisfies the above heat resistance and purity is not particularly limited, but bisphenol A type (or AD type, S type, F type) glycidyl ether, water-added bisphenol A type Glycidyl ether, ethylene oxide adduct bisphenol A and / or F type glycidyl ether, propylene oxide adduct bisphenol A and / or F type glycidyl ether, phenol novolac resin glycidyl ether, cresol novolac resin glycidyl ether, bisphenol A novolak Glycidyl ether of resin, glycidyl ether of naphthalene resin, trifunctional (or tetrafunctional) glycidyl ether, glycidyl ether of dicyclopentadienephenol resin, glycidyl of dimer acid Esters, those in which a functional type (or tetrafunctional) glycidyl amines of glycidyl amine and naphthalene resin such as a raw material.

In particular, in order to improve thermocompression bonding, low stress properties, and adhesiveness, the number of epoxy groups and ethylenically unsaturated groups is preferably 3 or less, respectively, and in particular, the number of ethylenically unsaturated groups is 2. It is preferable that it is one or less. Although it does not specifically limit as such a compound, The compound etc. which are represented by following General formula (1), (2), (3), (4) or (5) are used preferably. In the following general formulas (1) to (5), R ¹² and R ¹⁶ represent a hydrogen atom or a methyl group, R ¹⁰ , R ¹¹ , R ¹³ and R ¹⁴ represent a divalent organic group, R ¹⁵ , R ¹⁷ and R ¹⁸ represent an organic group having an epoxy group or an ethylenically unsaturated group. f represents an integer. f is 1-10, for example.

  The amount of the monofunctional (meth) acrylate is preferably 20 to 100% by mass, more preferably 40 to 100% by mass, and 50 to 100% by mass with respect to the (B) radiation polymerizable compound. Most preferably. By adjusting the amount of the monofunctional (meth) acrylate to the above-mentioned amount, it is possible to improve the adhesion and thermocompression bonding with the adherend after the B-stage.

  (B) The radiation polymerizable compound may contain a bifunctional or higher functional (meth) acrylate. Such acrylates are not particularly limited, but are diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate. , Trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6- Hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol Laacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl acrylate 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,2-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, tris (β -Hydroxyethyl) isocyanurate triacrylate, compound represented by the following general formula (6), urethane acrylate, urea Examples thereof include tan methacrylate and urea acrylate.

In the general formula (6), R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a methyl group, and g and h each independently represent an integer of 1 to 20.

  These radiation polymerizable compounds can be used singly or in combination of two or more. Among them, the radiation polymerizable compound having a glycol skeleton represented by the general formula (6) is preferable in that it can sufficiently impart solvent resistance after curing, has low viscosity, and has a high 5% mass reduction temperature. .

  By using a radiation polymerizable compound having a high functional group equivalent, it is possible to more effectively suppress the stress applied to the semiconductor wafer (lower stress) and suppress the warpage of the semiconductor wafer (lower warpage). The radiation-polymerizable compound having a high functional group equivalent preferably has a polymerization functional group equivalent of 200 eq / g or more, more preferably 300 eq / g or more, and most preferably 400 eq / g or more. By using a radiation-polymerizable compound having an ether skeleton, urethane group and / or isocyanuric group having a polymerization functional group equivalent of 200 eq / g or more, the adhesiveness of the photosensitive adhesive is improved, and the stress and the warpage are reduced. It becomes possible. A radiation polymerizable compound having a polymerization functional group equivalent of 200 eq / g or more and a radiation polymerizable compound having a polymerization functional group equivalent of less than 200 eq / g may be used in combination.

  The amount of the (B) radiation polymerizable compound is preferably 10 to 95% by mass with respect to the total amount of the photosensitive adhesive, and more preferably 20 to 90% by mass from the viewpoint of wetting and spreading at the time of chip pressing. Preferably, it is most preferably 40 to 90% by mass from the viewpoint of shape retention after B-stage formation. When the component (B) is less than 10% by mass, the tack force after B-stage formation tends to increase, and when it exceeds 95% by mass, the adhesive strength after thermosetting tends to decrease. The upper limit and lower limit of the amount of the radiation polymerizable compound are 10% by mass, 20% by mass, 40% by mass, 56.7% by mass, 66% by mass, 90% by mass or 95% with respect to the total amount of the photosensitive adhesive. It may be mass%.

  (B) The radiation-polymerizable compound is preferably liquid at room temperature (15 ° C. to 30 ° C.), and the viscosity is preferably 5000 mPa · s or less in consideration of the removal of the photosensitive adhesive from the mesh printing plate. When considering further flattening due to self-flow after printing, it is more preferably 3000 mPa · s or less. When the viscosity exceeds 5000 mPa · s, the viscosity of the photosensitive adhesive tends to increase and the printability tends to decrease.

  (B) The radiation-polymerizable compound preferably has a 5% mass reduction temperature of 120 ° C. or higher, more preferably 150 ° C. or higher, and even more preferably 180 ° C. or higher. Here, the 5% mass reduction temperature refers to a radiation-polymerizable compound using a differential thermothermal gravimetric simultaneous measurement apparatus (manufactured by SII Nano Technology: TG / DTA6300), a temperature rising rate of 10 ° C./min, and a nitrogen flow (400 ml). / Min) is a 5% mass loss temperature when measured under. By applying a radiation polymerizable compound having a high 5% mass reduction temperature, it is possible to suppress volatilization of the unreacted radiation polymerizable compound during thermocompression bonding or thermosetting.

  (C) The photopolymerization initiator (photoinitiator) is preferably one having a molecular extinction coefficient of 100 ml / g · cm or more with respect to light having a wavelength of 365 nm, from the viewpoint of improving the sensitivity of photopolymerization, and 200 ml / g · cm. The above is more preferable. As for the molecular extinction coefficient, a 0.001% by mass acetonitrile solution of the sample is prepared, and the absorbance of this solution is measured using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, “U-3310” (trade name)). Is required.

  Examples of such component (C) include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one. 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1, 2,4-diethylthioxanthone, 2-ethylanthraquinone and phenanthrenequinone Benzyl derivatives such as aromatic ketones, benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole Dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- ( -Methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole Dimer and 2,4,5-triarylimidazole dimer such as 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine and 1,7-bis ( Acridine derivatives such as 9,9'-acridinyl) heptane, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and bis (2,4,6, -trimethylbenzoyl) -phenyl Examples include bisacylphosphine oxides such as phosphine oxide, and compounds having maleimide. . These can be used individually by 1 type or in combination of 2 or more types.

  Among the above photopolymerization initiators, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-in terms of solubility in a photosensitive adhesive containing no solvent. 1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one and 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane -1-one is preferably used. Furthermore, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2 is that the photosensitive adhesive layer can be B-staged by exposure even in an air atmosphere. -Dimethoxy-1,2-diphenylethane-1-one and 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one are preferably used.

  (C) component may contain the photoinitiator which expresses the function which accelerates | stimulates superposition | polymerization and / or reaction of an epoxy resin by irradiation of a radiation. Examples of such a photoinitiator include a photobase generator that generates a base by irradiation, a photoacid generator that generates an acid by irradiation, and the photobase generator is particularly preferable.

  By using a photobase generator, the adhesiveness (high temperature adhesiveness) and moisture resistance of the photosensitive adhesive to the adherend can be further improved. This is because the base generated from the photobase generator efficiently acts as a curing catalyst for the epoxy resin, so that the crosslinking density can be further increased, and the generated curing catalyst corrodes the substrate and the like. There are few. By containing a photobase generator in the photosensitive adhesive, the crosslink density can be improved, and the outgas during standing at high temperature can be further reduced. Furthermore, it is considered that the temperature of the curing process can be lowered and shortened.

  The photobase generator can be used without particular limitation as long as it is a compound that generates a base upon irradiation with radiation. As the base to be generated, a strongly basic compound is preferable in terms of reactivity and curing speed.

  Examples of the base generated during irradiation with radiation include imidazole derivatives such as imidazole, 2,4-dimethylimidazole and 1-methylimidazole, piperazine derivatives such as piperazine and 2,5-dimethylpiperazine, piperidine and 1,2 and 1,2. -A piperidine derivative such as dimethylpiperidine, a proline derivative, a trialkylamine derivative such as trimethylamine, triethylamine and triethanolamine, an amino group or an alkylamino group at the 4-position such as 4-methylaminopyridine and 4-dimethylaminopyridine Pyridine derivatives, pyrrolidine derivatives such as pyrrolidine and n-methylpyrrolidine, dihydropyridine derivatives, triethylenediamine and alicyclic rings such as 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU) Derivatives, as well as, benzyl methyl amine, benzyl amine derivatives such as benzyl dimethyl amine and benzyl diethyl amine.

  Examples of photobase generators that generate a base as described above upon irradiation with radiation include, for example, Journal of Photopolymer Science and Technology 12, 313-314 (1999), Chemistry of Materials 11, 170-176 (19 Can be used. Since these produce a highly basic trialkylamine upon irradiation with actinic rays (radiation), they are optimal for curing epoxy resins.

  As the photobase generator, carbamic acid derivatives described in Journal of American Chemical Society 118, 12925 (1996), Polymer Journal 28, 795 (1996), and the like can also be used.

  Examples of photobase generators that generate a base upon irradiation with actinic rays include 2,4-dimethoxy-1,2-diphenylethane-1-one, 1,2-octanedione, and 1- [4- (phenylthio) -2. -(O-benzoyloxime)] and ethanone, and oxime derivatives such as 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, which is commercially available as a photoradical generator, 2- Methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Thanong -1, hexaarylbisimidazole derivatives (halogen, alkoxy group, substituent such as a nitro group and a cyano group may be substituted in the phenyl group), and can be used benzisoxazole pyrazolone derivatives.

  As the photobase generator, a compound in which a group capable of generating a base is introduced into the main chain and / or side chain of the polymer may be used. The molecular weight in this case is preferably a weight average molecular weight of 1,000 to 100,000, more preferably 5,000 to 30,000 from the viewpoints of adhesiveness, fluidity and heat resistance as a photosensitive adhesive.

  Since the photobase generator does not show reactivity with the epoxy resin when not exposed to light, the storage stability at room temperature is very excellent.

  The amount of the photopolymerization initiator may be 5 parts by mass or more or 1 part by mass or more with respect to 100 parts by mass of the radiation polymerizable compound. The amount of the photopolymerization initiator may be 0.1 parts by mass or less or 1 part by mass or less with respect to 100 parts by mass of the radiation polymerizable compound.

  The photosensitive adhesive according to this embodiment can be used in combination with a sensitizer as necessary. Examples of the sensitizer include camphorquinone, benzyl, diacetyl, benzyldimethyl ketal, benzyl diethyl ketal, benzyl di (2-methoxyethyl) ketal, 4,4′-dimethylbenzyl-dimethyl ketal, anthraquinone, 1-chloroanthraquinone. 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-bromoanthraquinone, thioxanthone, 2-isopropylthioxanthone, 2-nitrothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chloro-7-trifluoromethylthioxanthone, Oxanthone-10,10-dioxide, thioxanthone-10-oxide, benzoin methyl ether, benzoin ethyl ether, isopropyl ether, benzoin isobutyl ether, benzophenone, bis (4-dimethylaminophenyl) ketone, 4,4′-bisdiethylaminobenzophenone and The compound containing an azide group is mentioned. These can be used alone or in combination of two or more.

  In the photosensitive adhesive which concerns on this embodiment, you may contain the thermoplastic resin (D) at the point which improves low stress property, adhesiveness with a to-be-adhered body, and thermocompression bonding property. The glass transition temperature (Tg) of the component (D) is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower, and most preferably 80 ° C. or lower. preferable. When this Tg exceeds 150 ° C., the viscosity of the photosensitive adhesive tends to increase. Further, a high temperature of 150 ° C. or higher is required for thermocompression bonding to the adherend, and the semiconductor wafer tends to be warped.

  Here, “Tg” means the main dispersion peak temperature of the (D) component formed into a film. Using a viscoelasticity analyzer “RSA-2” (trade name) manufactured by Rheometrics Co., Ltd., measurement was performed under the conditions of a film thickness of 100 μm, a heating rate of 5 ° C./min, a frequency of 1 Hz, and a measuring temperature of −150 to 300 ° C. The tan δ peak temperature observed near Tg is the main dispersion peak temperature.

  It is preferable that the weight average molecular weight of (D) component is controlled within the range of 5000-500000, and it is more preferable that it is 10000-300000 in the point which can make thermocompression-bonding property and high temperature adhesiveness highly compatible. Here, the “weight average molecular weight” means a weight average molecular weight when measured in terms of polystyrene using high performance liquid chromatography “C-R4A” (trade name) manufactured by Shimadzu Corporation.

  As the component (D), polyester resin, polyether resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polyurethane resin, polyurethaneimide resin, polyurethaneamideimide resin, siloxane polyimide resin, polyesterimide resin, these Copolymer, precursors thereof (polyamide acid, etc.), polybenzoxazole resin, phenoxy resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, polyester resin, polyether resin, polycarbonate resin, polyether ketone Examples thereof include a resin, a (meth) acrylic copolymer having a weight average molecular weight of 10,000 to 1,000,000, a novolac resin, and a phenol resin. These can be used alone or in combination of two or more. In addition, the main chain and / or side chain of these resins may be provided with a glycol group such as ethylene glycol and propylene glycol, a carboxyl group, and / or a hydroxyl group.

  Among these, it is preferable that (D) component is resin which has an imide group from a high temperature adhesiveness and a heat resistant viewpoint. Examples of the resin having an imide group include polyimide resins, polyamideimide resins, polyetherimide resins, polyurethaneimide resins, polyurethaneamideimide resins, siloxane polyimide resins, polyesterimide resins, and copolymers thereof. The polyimide resin can be obtained by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method. That is, in the organic solvent, tetracarboxylic dianhydride and diamine are equimolar, or if necessary, the total amount of diamine is preferably 0.00 with respect to the total 1.0 mol of tetracarboxylic dianhydride. The composition ratio is adjusted in the range of 5 to 2.0 mol, more preferably 0.8 to 1.0 mol (the order of addition of each component is arbitrary), and the addition reaction is performed at a reaction temperature of 80 ° C. or lower, preferably 0 to 60 ° C. . As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide resin precursor, is generated. The tetracarboxylic dianhydride is preferably purified by recrystallization with acetic anhydride in order to suppress deterioration of various characteristics of the photosensitive adhesive.

  About the composition ratio of tetracarboxylic dianhydride and diamine in the condensation reaction, when the total of diamine exceeds 2.0 mol with respect to the total 1.0 mol of tetracarboxylic dianhydride, The amount of the polyimide oligomer having an amine terminal tends to increase. Furthermore, the weight average molecular weight of the polyimide resin is lowered, and various characteristics including the heat resistance of the photosensitive adhesive tend to be insufficient. On the other hand, when the total of diamine is less than 0.5 mol with respect to 1.0 mol of tetracarboxylic dianhydride, the amount of polyimide resin oligomer having an acid terminal (carboxyl terminal) tends to increase. Furthermore, the weight average molecular weight of the polyimide resin is lowered, and various characteristics including the heat resistance of the photosensitive adhesive tend to be insufficient.

  The polyimide resin can be obtained by dehydrating and ring-closing the reaction product (polyamic acid). The dehydration ring closure can be performed by a thermal ring closure method in which heat treatment is performed, a chemical ring closure method using a dehydrating agent, or the like.

  There is no restriction | limiting in particular as tetracarboxylic dianhydride used as a raw material of a polyimide resin, For example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) ) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracar Acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetra Carboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetra Carboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2, 3, 6, 7- Trachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride Anhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetra Carboxylic dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) Methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1, 3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2 , 3,4-Butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid Dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2 , 2]-Oct -7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (3 4-dicarboxyphenyl) phenyl] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) ) Phenyl] hexafluoropropane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic acid) Anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuran) ) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride and tetracarboxylic acid represented by the following general formula (7) An acid dianhydride is mentioned. In the following general formula (7), a represents an integer of 2 to 20.

  The tetracarboxylic dianhydride represented by the general formula (7) can be synthesized from, for example, trimellitic anhydride monochloride and the corresponding diol. Specifically, 1,2- (ethylene) bis (trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5 -(Pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) Bis (trimellitic anhydride), 1,9- (nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodecamethylene) bis (trimellitic anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride) and 1,18- (octadecamethylene) bis (g Mellitate anhydrides).

  The tetracarboxylic dianhydride is a tetracarboxylic dianhydride represented by the following formula (8) or (9) from the viewpoint of imparting good solubility in solvents and moisture resistance and transparency to light having a wavelength of 365 nm. Anhydrides are preferred.

  The above tetracarboxylic dianhydrides can be used singly or in combination of two or more.

  The component (D) can further use a carboxyl group and / or a phenolic hydroxyl group-containing polyimide resin in terms of increasing the adhesive strength. The diamine used as a raw material for the carboxyl group and / or hydroxyl group-containing polyimide resin preferably contains an aromatic diamine represented by the following formula (10), (11), (12) or (13).

  There is no restriction | limiting in particular as other diamine used as a raw material of the said polyimide resin, For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'- diaminodiphenyl ether, 3,4'-diaminodiphenyl ether 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis (4-amino-3,5-dimethylphenyl) methane, bis ( 4-amino-3,5-diisopropylphenyl) methane, 3,3′-diaminodiphenyldifluoromethane, 3,4′-diaminodiphenyldifluoromethane, 4,4′-diaminodiphenyldifluoromethane, 3,3′-diaminodiphenyl Sulfo 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfide, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 3,3 ′ -Diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 '-(3,4'-diaminodiphenyl) Propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2 -Bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) Benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3 , 4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- ( 3-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminoenoxy) phenyl) sulfide, bis (4- (4-aminoenoxy) phenyl) sulfide, bis (4- (3-amino Noenoxy) phenyl) sulfone, bis (4- (4-aminoenoxy) phenyl) sulfone, aromatic diamines such as 3,3′-dihydroxy-4,4′-diaminobiphenyl and 3,5-diaminobenzoic acid, 1,3 -Bis (aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane, aliphatic ether diamine represented by the following general formula (14), and siloxane represented by the following general formula (15) Examples include diamines.

Among the diamines, aliphatic ether diamines represented by the following general formula (14) are preferable, and ethylene glycol and / or propylene glycol-based diamines are more preferable in terms of imparting compatibility with other components. In the following general formula (14), R ¹ , R ² and R ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and b represents an integer of 2 to 80.

  Specific examples of such aliphatic ether diamines include Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED-900, ED-2000, and EDR manufactured by Sun Techno Chemical Co., Ltd. -148, BASF (manufactured) aliphatic amines such as polyetheramines D-230, D-400 and D-2000. These diamines are preferably 20 mol% or more of the total diamines, and are compatible with other compounding components such as (A) thermosetting resins and (B) radiation-polymerizable compounds, and thermocompression bonding properties and high temperatures. It is more preferably 50 mol% or more from the viewpoint that the adhesiveness is highly compatible.

As said diamine, the siloxane diamine represented by following General formula (15) is preferable at the point which provides the adhesiveness and adhesiveness in room temperature. In the following general formula (15), R ⁴ and R ⁹ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and d represents an integer of 1 to 5.

  These diamines are preferably 0.5 to 80 mol% of the total diamine, and more preferably 1 to 50 mol% from the viewpoint of achieving both high thermocompression bonding and high temperature adhesiveness. If the amount is less than 0.5 mol%, the effect of adding siloxane diamine is reduced. If the amount exceeds 80 mol%, the compatibility with other components and high-temperature adhesiveness tend to be reduced.

  Specifically, as the siloxane diamine represented by the general formula (15), it is assumed that d in the formula (15) is 1, 1,1,3,3-tetramethyl-1,3-bis (4- Aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (2- Aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (2- Aminoethyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3- Aminobutyl) disiloxane and 1,3-dimethyl-1 3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane, and the like. Assuming that d in the formula (15) is 2, 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetra Phenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) Trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy -1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1, 5,5-tetramethyl-3,3-dimethoxy -1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3 , 5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane, etc. Is mentioned.

  The diamine mentioned above can be used individually by 1 type or in combination of 2 or more types.

  The said polyimide resin can be used individually by 1 type or in mixture (blend) of 2 or more types as needed.

  As described above, when determining the composition of the polyimide resin, it is preferably designed so that the Tg of the polyimide resin is 150 ° C. or less. As the diamine that is a raw material of the polyimide resin, the general formula (14) It is particularly preferred to use the aliphatic ether diamine represented.

  By synthesizing a monofunctional acid anhydride such as a compound represented by the following formula (16), (17) or (18) and / or a monofunctional amine into the condensation reaction solution during the synthesis of the polyimide resin, a polymer is obtained. A functional group other than acid anhydride or diamine can be introduced at the terminal. Further, this can lower the molecular weight of the polymer, reduce the viscosity of the photosensitive adhesive, and improve the thermocompression bonding property.

  The component (D) may have a functional group having a function of accelerating curing of an epoxy resin such as imidazole as its main chain and / or side chain. For example, an imidazole-containing polyimide can be obtained as follows. A part of the diamine component shown above can be obtained using an imidazole group-containing diamine as represented by the following structural formula.

  From the point that the polyimide resin can be uniformly B-staged, the transmittance for light having a wavelength of 365 nm when the thickness is formed to 30 μm is preferably 10% or more, and can be B-staged with a lower exposure amount. And more preferably 20% or more. Such a polyimide resin is represented by, for example, an acid anhydride represented by the general formula (7), an aliphatic ether diamine represented by the general formula (14), and / or the general formula (15). It can be synthesized by reacting with siloxane diamine.

  (D) As the thermoplastic resin, it is preferable to use a liquid thermoplastic resin that is liquid at room temperature (25 ° C.) in terms of suppressing an increase in viscosity and further reducing undissolved residue in the photosensitive adhesive. Such a thermoplastic resin can be reacted by heating without using a solvent, and in the case of a photosensitive adhesive that does not apply a solvent as in this embodiment, the solvent removal process is reduced, and the remaining solvent is reduced. This is useful in terms of reducing the reprecipitation process. Further, the liquid thermoplastic resin can be easily taken out from the reaction furnace. Such a liquid thermoplastic resin is not particularly limited, but is a rubbery polymer such as polybutadiene, acrylonitrile-butadiene oligomer, polyisoprene and polybutene, polyolefin, acrylic polymer, silicone polymer, polyurethane, polyimide, and polyamideimide. Is mentioned. Of these, a polyimide resin is preferably used.

  The liquid polyimide resin can be obtained, for example, by reacting the acid anhydride with an aliphatic ether diamine or siloxane diamine. As a synthesis method, an acid anhydride is dispersed in an aliphatic ether diamine or siloxane diamine without adding a solvent and heated.

  The photosensitive adhesive according to the present embodiment is subjected to exposure using a high-precision parallel exposure machine (“EXM-1172-B-∞” (trade name) manufactured by Oak Manufacturing Co., Ltd.), and then the lowest melting at 20 ° C. to 300 ° C. A photosensitive adhesive having a viscosity of 30000 Pa · s or less is preferable. Instead of the above high-accuracy parallel exposure machine, a parallel exposure machine (manufactured by Luminous Co., Ltd., “ML-210FM mask aligner” (trade name)) may be used.

In this specification, the “minimum melt viscosity” is measured using a viscoelasticity measuring device ARES (manufactured by Rheometrics Scientific FP Co., Ltd.) after exposing the sample with light having a light amount of 1000 mJ / cm ^2. The minimum value of the melt viscosity at 20 ° C. to 300 ° C. is shown. Note that a parallel plate having a diameter of 8 mm is used as the measurement plate. The temperature rise rate is 5 ° C./min, the measurement temperature is 20 ° C. to 300 ° C., and the frequency is 1 Hz.

  The minimum melt viscosity is preferably 20000 Pa · s or less, more preferably 18000 Pa · s or less, and even more preferably 15000 Pa · s or less. By having the minimum melt viscosity within the above range, sufficient low-temperature thermocompression bonding property can be ensured, and good adhesion can be imparted even to a substrate having unevenness. The lower limit of the minimum melt viscosity is not particularly provided, but is preferably 10 Pa · s or more from the viewpoint of handleability.

  As the photosensitive adhesive according to the present embodiment, a thermal radical generator can be used as necessary. The thermal radical generator is preferably an organic peroxide. The organic peroxide preferably has a 1 minute half-life temperature of 80 ° C. or higher, more preferably 100 ° C. or higher, and most preferably 120 ° C. or higher. The organic peroxide is selected in consideration of the preparation conditions of the photosensitive adhesive, the film forming temperature, the curing (bonding) conditions, other process conditions, storage stability, and the like. Examples of usable organic peroxides include, but are not limited to, 2,5-dimethyl-2,5-di (t-butylperoxyhexane), dicumyl peroxide, t-butylperoxy- 2-ethylhexanate, t-hexylperoxy-2-ethylhexanate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylper Oxy) -3,3,5-trimethylcyclohexane and bis (4-t-butylcyclohexyl) peroxydicarbonate, and one of these may be used alone or two or more of them may be used in combination. . By containing the organic peroxide, the unreacted radiation-polymerizable compound remaining after the exposure can be reacted, and the outgas can be reduced (lower outgassing) and the adhesion can be increased.

  The amount of the thermal radical generator is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and most preferably 0.5 to 5% by mass with respect to the total amount of the radiation polymerizable compound. If it is less than 0.01% by mass, the curability is lowered and the effect of addition becomes small, and if it exceeds 5% by mass, the amount of outgas increases and the storage stability tends to be reduced.

  The thermal radical generator is not particularly limited as long as it has a half-life temperature of 80 ° C. or more for 1 minute. For example, perhexa 25B (manufactured by NOF Corporation), 2,5-dimethyl-2,5-di ( t-butylperoxyhexane) (1 minute half-life temperature: 180 ° C.), park mill D (manufactured by NOF Corporation) and dicumyl peroxide (1 minute half-life temperature: 175 ° C.).

  The photosensitive adhesive according to the present embodiment is prohibited from polymerization of quinones, polyphenols, phenols, phosphites, sulfurs, etc. in order to impart storage stability, process adaptability or antioxidant properties. An agent or an antioxidant may be further added as long as the curability of the photosensitive adhesive is not impaired.

  Furthermore, the photosensitive adhesive according to this embodiment may contain a filler as appropriate. Examples of the filler include metal fillers such as silver powder, gold powder, copper powder and nickel powder, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, Examples include inorganic fillers such as aluminum oxide, aluminum nitride, crystalline silica, amorphous silica, boron nitride, titania, glass, iron oxide and ceramic, and organic fillers such as carbon and rubber fillers, types and shapes, etc. It can be used without any particular limitation.

  The filler can be used properly according to the desired function. For example, the metal filler is added for the purpose of imparting conductivity, thermal conductivity, thixotropy and the like to the photosensitive adhesive. Non-metallic inorganic filler is added for the purpose of imparting thermal conductivity, low thermal expansion and low hygroscopicity to the photosensitive adhesive layer, and the organic filler is for the purpose of imparting toughness to the photosensitive adhesive layer. Added.

  These metal fillers, inorganic fillers, or organic fillers can be used singly or in combination of two or more. Among these, a metal filler or an inorganic filler is preferable in that it can provide conductivity, thermal conductivity, or low moisture absorption characteristics required for an adhesive material for a semiconductor device, and an insulating filler is preferable in that it can provide insulation. Among inorganic fillers or insulating fillers, silica fillers are more preferable because they have good dispersibility with respect to the photosensitive adhesive and can impart high adhesive strength during heating.

  The filler preferably has an average particle size of 10 μm or less and a maximum particle size of 30 μm or less, more preferably an average particle size of 5 μm or less and a maximum particle size of 20 μm or less. If the average particle size exceeds 10 μm and the maximum particle size exceeds 30 μm, the effect of improving fracture toughness tends to be insufficient. The lower limit of the average particle size and the maximum particle size is not particularly limited, but usually both are 0.001 μm or more.

  Although the quantity of the said filler is determined according to the characteristic or function to provide, 0-50 mass% is preferable with respect to the sum total of a resin component ((A) component etc.) and a filler, and 1-40 mass% is more preferable. 3 to 30% by mass is more preferable. By increasing the amount of filler, low alpha, low moisture absorption, and high elastic modulus can be achieved, and dicing performance (cutability with a dicer blade), wire bonding performance (ultrasonic efficiency), and adhesive strength during heating are effectively improved. Can be made.

  When the amount of the filler is increased more than necessary, the viscosity of the photosensitive adhesive tends to increase or the thermocompression bonding property of the photosensitive adhesive tends to be impaired. Therefore, the amount of the filler is preferably within the above range. The optimum amount of filler is determined in order to balance the required properties. Mixing and kneading in the case of using a filler can be carried out by appropriately combining ordinary stirrers, crackers, three-rollers, ball mills and other dispersers.

  Various coupling agents can also be added to the photosensitive adhesive according to the present embodiment in order to improve interfacial bonding between different materials. Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent. Among them, a silane coupling agent is preferable because of its high effect, and a compound having a thermosetting functional group such as an epoxy group and a radiation polymerizable functional group such as methacrylate and / or acrylate is more preferable. The boiling point and / or decomposition temperature of the silane coupling agent is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and even more preferably 200 ° C. or higher. That is, a silane coupling agent having a boiling point of 200 ° C. or higher and / or a decomposition temperature and having a thermosetting functional group such as an epoxy group and a radiation polymerizable functional group such as methacrylate and / or acrylate is most preferably used. It is done. The amount of the coupling agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the photosensitive adhesive to be used, from the viewpoint of the effect, heat resistance and cost.

  In the photosensitive adhesive according to the present embodiment, an ion scavenger can be further added in order to adsorb ionic impurities and improve insulation reliability during moisture absorption. Such an ion scavenger is not particularly limited. For example, triazine thiol compound, a compound known as a copper damage preventer for preventing copper from being ionized and dissolved, such as a phenol-based reducing agent, Inorganic compounds such as bismuth-based, antimony-based, magnesium-based, aluminum-based, zirconium-based, calcium-based, titanium-based, zuzu-based, and mixed systems thereof. Specific examples include, but are not limited to, inorganic ion scavengers manufactured by Toa Gosei Co., Ltd., trade names, IXE-300 (antimony), IXE-500 (bismuth), IXE-600 (antimony, bismuth mixed). ), IXE-700 (magnesium and aluminum mixed system), IXE-800 (zirconium series), IXE-1100 (calcium series), and the like. These can be used individually by 1 type or in mixture of 2 or more types. The amount of the ion scavenger is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the photosensitive adhesive from the viewpoint of the effect of addition, heat resistance, cost, and the like.

  From the viewpoint of stably supplying the photosensitive adhesive to the opening of the mesh printing plate before printing, from the viewpoint of removal of the photosensitive adhesive from the mesh opening during printing, and after printing The thixotropy index of the photosensitive adhesive is 1.0 to 3.0 from the viewpoint of flattening the bubbles and mesh marks of the photosensitive adhesive layer by spontaneously flowing the photosensitive adhesive. Is preferred. When the thixotropy index is 1.0 or more, there is a tendency that generation of sagging or the like in the photosensitive adhesive supplied and applied by a printing method can be suppressed and the printed shape can be kept good. Furthermore, when the thixotropy index is 3.0 or less, it tends to be possible to suppress the occurrence of “chips” or blurring in the photosensitive adhesive supplied and applied by the printing method. The upper and lower limit values of the thixotropy index of the photosensitive adhesive may be 1.0, 1.2, 1.3, or 3.0.

  The viscosity at 25 ° C. of the photosensitive adhesive is such that the photosensitive adhesive is supplied from the mesh opening during printing from the viewpoint of handling the photosensitive adhesive such as supplying the photosensitive adhesive onto the printing plate at the time of work. It is preferable that the pressure is 1 to 100 Pa · s from the viewpoint of flattening the bubbles and mesh marks of the photosensitive adhesive layer after the printing by spontaneously flowing the photosensitive adhesive from the viewpoint of omission. The upper and lower limits of the viscosity of the photosensitive adhesive at 25 ° C. may be 1 Pa · s, 8.5 Pa · s, 12.8 Pa · s, 16.0 Pa · s, or 100 Pa · s.

  The said viscosity shall be a value when it measures on conditions of 3 degree cone, 25 degreeC, and rotation speed 0.5rpm using an E-type rotational viscometer (made by Tokyo Keiki). The thixotropy index is defined by a ratio between a value measured with an E-type rotational viscometer at 25 ° C. and a rotational speed of 1 rpm and a value measured at 25 ° C. and a rotational speed of 10 rpm (thixotropic index). = (Viscosity at 1 rpm) / (viscosity at 10 rpm)).

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

(Adjustment of photosensitive adhesive)
First, a thermosetting resin and a radiation polymerizable compound were stirred and dissolved in a four-necked separable flask installed in an oil bath while heating to 60 ° C. in a nitrogen atmosphere. A thermosetting initiator and a photopolymerization initiator were added to the obtained solutions, respectively, placed in a raking machine, kneaded, and then defoamed and kneaded at 5 Torr or less for 1 hour. Furthermore, the viscosity was adjusted by adding a radiation-polymerizable compound and defoaming kneading, and a photosensitive adhesive having a ratio of each component shown in Table 1 was obtained. Table 1 shows the viscosity and thixotropy index at 25 ° C. of each photosensitive adhesive.

(Formation of photosensitive adhesive layer)
Using the obtained photosensitive adhesive, an MK-838SV printing machine (manufactured by Minami Co., Ltd.) on which a V-screen V160 mesh printing plate (manufactured by NBC Meshtec Co., Ltd.) was installed was used. On the back surface of the silicon wafer, a 6 inch φ circular print was applied. When the state of the photosensitive adhesive after printing was visually confirmed, it was found that there was no blurring and a uniform photosensitive adhesive layer could be provided.

(Measurement of tack force on the surface of the photosensitive adhesive layer after B-stage)
As Examples 1-4, the parallel exposure machine (the product made by Luminous, "ML-210FM mask aligner" (brand name)) is used for the photosensitive adhesive layer formed on the silicon wafer by the screen printing method. Exposure was performed at 1000 mJ / cm ² in a nitrogen atmosphere, and the photosensitive adhesive layer was changed to B stage. Further, as Comparative Example 1, a silicon wafer printed with the same photosensitive adhesive as that in Example 1 was prepared, put into a dryer at 100 ° C. for 1 hour, and B-staged by heating. After B-stage, using a probe tacking tester manufactured by Reska, 30 ° C. under conditions of probe diameter: 5.1 mm, peeling speed: 10 mm / s, contact load: 100 gf / cm ² , contact time: 1 s The surface tack force of the photosensitive adhesive layer was measured. Table 1 shows the surface tack force after the B stage.

(Observation of warpage of silicon wafer after B-stage)
As a result of observing the silicon wafer after B-stage obtained by the above “measurement of the surface tack force of the photosensitive adhesive layer after B-stage”, the photosensitive adhesive layer obtained in Examples 1 to 4 was No warpage was found in the formed silicon wafer. However, in the silicon wafer formed with the photosensitive adhesive layer obtained in Comparative Example 1, warpage of the silicon wafer accompanying heating was observed, and the height difference between the edge and the center of the silicon wafer was about 1.5 cm. there were. Table 1 shows the observation results of the warpage of the silicon wafer after the B stage.

(Pickup property)
After dicing tape is laminated on the silicon wafer side of the silicon wafer on which the photosensitive adhesive layer is formed by the screen printing method and placed on the wafer ring, a dicing machine ("DAD-3220" (product name) manufactured by DISCO Corporation) ) Was used for dicing to 10 × 10 mm square. In Examples 1 to 4, when the state of the silicon wafer after dicing was confirmed, dicing was possible without a lack of silicon chips. Further, when 10 silicon chips were picked up from the dicing tape, there was no transfer of the photosensitive adhesive to the dicing tape, and the pick-up property was good. On the other hand, in Comparative Example 1, the tacking force of the photosensitive adhesive layer after the B-stage was too strong and dicing could not be performed.

(Shear strength measurement)
A silicon chip with an adhesive layer (5 × 5 mm square) obtained in the same manner as above was thermocompression-bonded (200 gf, 120 ° C., 3 seconds) on a separately prepared silicon chip (8 × 8 mm square), and placed in an oven. At 180 ° C. for 1 hour. The shear strength at 250 ° C. was measured for the obtained sample using an automatic adhesive strength tester (manufactured by Arctech Co., Ltd., “DAGE SERIES 4000” (trade name)). The measurement results are as shown in Table 1.

Each symbol in Table 1 has the following meaning.
YDCN700-7: Toto Kasei Co., Ltd., cresol novolac type epoxy resin YDF-8170C: Toto Kasei Co., Ltd., bisphenol F type epoxy resin EP1032H60: JER Co., Ltd., tris (hydroxyphenyl) methane type solid epoxy resin Aronix M- 140: Toagosei Co., Ltd., N-acryloyloxyethyl hexahydrophthalimide FA-220M: Hitachi Chemical Co., Ltd., polyethylene glycol # 200 dimethacrylate I-819: Ciba Japan Co., Ltd., phenyl bis (2,4 , 6-Trimethylbenzoyl) -phosphine oxide I-379EG: Ciba Japan, 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one 1B2PZ : Shikoku Chemicals Co., Ltd. - benzyl-2-phenylimidazole.

DESCRIPTION OF SYMBOLS 1 ... Outer frame of printing plate, 2 ... Part embedded in resin in mesh printing plate, 3 ... Opening in mesh printing plate, 4 ... Squeegee, 5 ... Photosensitive adhesive, 6 ... Semiconductor wafer, 7 ... Photosensitive Adhesive layer, 8 ... photosensitive adhesive layer B-staged by exposure, 9 ... frame, 10 ... dicing film, 11 ... semiconductor chip with adhesive layer, 12 ... dicing blade, 13a ... first stage semiconductor Chip, 13b ... second stage semiconductor chip, 14 ... support member, 15 ... sealing material, 16 ... photosensitive adhesive layer for joining first stage semiconductor chip and support member, 17 ... second stage semiconductor A photosensitive adhesive layer for bonding the chip and the first-stage semiconductor chip, 18... Bonding wire, 20... Semiconductor wafer with adhesive layer.

Claims (9)

Applying a photosensitive adhesive to the entire surface of one of the semiconductor wafers by a screen printing method to form a photosensitive adhesive layer;
A step of exposing the photosensitive adhesive layer to a B-stage by exposure;
A method for manufacturing a semiconductor wafer with an adhesive layer, comprising:   The manufacturing method of Claim 1 in which the said photosensitive adhesive agent contains a thermosetting resin, a radiation polymerizable compound, and a photoinitiator.   The manufacturing method according to claim 1 or 2, wherein the photosensitive adhesive further contains a thermosetting initiator.   The viscosity at 25 ° C of the photosensitive adhesive is 1 to 100 Pa · s, and the thixotropy index of the photosensitive adhesive is 1.0 to 3.0. The manufacturing method as described.   The photosensitive adhesive for using for the manufacturing method of Claim 1 containing a thermosetting resin, a radiation polymerizable compound, and a photoinitiator.   The photosensitive adhesive according to claim 5, further comprising a thermosetting initiator.   The photosensitive adhesive of Claim 5 or 6 whose viscosity in 25 degreeC is 1-100 Pa.s and whose thixotropy index is 1.0-3.0. A step of obtaining a semiconductor chip with an adhesive layer by separating the semiconductor wafer with an adhesive layer obtained by the manufacturing method according to any one of claims 1 to 4,
Bonding the semiconductor chip of the semiconductor chip with the adhesive layer to a support member or another semiconductor chip;
A semiconductor device obtained by a method comprising:   Photosensitive for screen printing, containing a thermosetting resin, a radiation polymerizable compound and a photopolymerization initiator, a viscosity at 25 ° C. of 1 to 100 Pa · s, and a thixotropic index of 1.0 to 3.0. adhesive.

Images