KR20130046426A - Method for manufacturing semiconductor wafer provided with adhesive layer, photosensitive adhesive, and semiconductor device - Google Patents

Abstract

The present invention includes a step of applying a photosensitive adhesive to the entire surface of one surface of a semiconductor wafer to form a photosensitive adhesive layer, and a step of B-stageting the photosensitive adhesive layer by exposure. A method for manufacturing a semiconductor wafer.

Description

Method for manufacturing semiconductor wafer with adhesive layer, photosensitive adhesive and semiconductor device {METHOD FOR MANUFACTURING SEMICONDUCTOR WAFER PROVIDED WITH ADHESIVE LAYER, PHOTOSENSITIVE ADHESIVE, AND SEMICONDUCTOR DEVICE}

TECHNICAL FIELD This invention relates to the manufacturing method of a semiconductor wafer with an adhesive bond layer, the photosensitive adhesive agent, and a semiconductor device. In more detail, the photosensitive adhesive agent for die bonding used as a bonding material (die bonding material) at the time of laminating | stacking semiconductor elements, such as IC and an LSI, support members, such as a lead frame and an insulating support substrate, or a semiconductor chip, and using the same A method for manufacturing a semiconductor wafer and a semiconductor device.

Die bonding in which an electrically conductive filler or an inorganic filler is added to an adhesive film using a specific polyimide resin or a specific polyimide resin as a bonding material for laminating semiconductor elements such as IC and LSI and a supporting member, or when bonding semiconductor chips together. The adhesive film for is known.

In recent years, the efficiency of the assembly process of a semiconductor device is performed by carrying out collectively on a semiconductor wafer (henceforth simply a "wafer"). In addition, the thickness of the wafer tends to be thin due to the stacking of semiconductor chips. Generally, the process of apply | coating the adhesive agent for die bonding to a semiconductor wafer by the process or spin coating method using an adhesive film is applied.

As a process using an adhesive film, an adhesive film is laminated on the entire surface of the semiconductor wafer, a supporting film for dicing is further laminated and separated into pieces by a dicing step, and the semiconductor chip on which the adhesive film is laminated is attached to a semiconductor substrate or a semiconductor chip. And the like can be mentioned.

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

In the process of using a thin wafer, the strength of the wafer tends to decrease. Therefore, after the back grinding process of the wafer, it is preferable to apply an adhesive for die bonding while bonding the back grinding tape to perform B stage formation.

Japanese Patent Publication No. 2008-98213 Japanese Patent Application Laid-Open No. 5-54262

However, when using an adhesive film, waste of an adhesive film tends to generate | occur | produce in parts other than a wafer in the process of laminating an adhesive film to a wafer. In addition, even in the case of using the spin coating method, it is necessary to supply the adhesive on the semiconductor wafer until the uniform adhesive layer is formed, and then discard the adhesive, and the waste of the adhesive is likely to occur.

Moreover, the heat resistance of a back grind tape is about 80 to 100 degreeC, and a back grind tape shrinks by heating at 100 degreeC or more. Shrinkage of the back grind tape may cause bending of the semiconductor wafer. Even with heating of 80 ° C. or less, the semiconductor wafer tends to bend during cooling after heating from the difference between the thermal expansion rate of the back grind tape and the thermal expansion rate of the semiconductor wafer.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has a uniform film thickness, enables the formation of an adhesive layer on a semiconductor wafer with little waste of adhesive, and furthermore, a semiconductor wafer resulting from heating for the B stage of the adhesive layer. Providing a method for producing a semiconductor wafer with an adhesive layer, a photosensitive adhesive agent used in such a manufacturing method, a semiconductor device provided with a semiconductor wafer with an adhesive layer which can be produced by such a manufacturing method, and a photosensitive adhesive for screen printing, which can avoid warpage. For the purpose of

With this adhesive layer including the process of apply | coating a photosensitive adhesive agent by the screen-printing method to the whole surface of a semiconductor wafer, and forming a photosensitive adhesive bond layer on the whole surface of a semiconductor wafer, and B-staging the photosensitive adhesive bond layer by exposure. A method for manufacturing a semiconductor wafer is provided.

According to the above-described manufacturing method of the present invention, the adhesive layer can be formed on the semiconductor wafer with a uniform film thickness and less waste of the adhesive, and further, the semiconductor wafer is warped due to heating for the B stage of the adhesive layer. Can be avoided.

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

The photosensitive adhesive may further contain a thermosetting initiator.

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

The photosensitive adhesive agent concerning this invention contains a thermosetting resin, a radiation polymeric compound, and a photoinitiator, and is used in order to form the photosensitive adhesive bond layer in the said manufacturing method.

The present invention further provides a step of separating the semiconductor wafer with an adhesive layer obtained by the manufacturing method according to the present invention to obtain a semiconductor chip having an adhesive layer, and attaching the semiconductor chip of the semiconductor wafer with an adhesive layer to a supporting member or another semiconductor chip. Provided is a semiconductor device obtained by a method including a step of bonding.

The present invention also provides a photosensitive adhesive for screen printing containing a thermosetting resin, a radiation polymerizable compound and a photopolymerization initiator, having a viscosity at 25 ° C. of 1 to 100 Pa · s and a thixotropy index of 1.0 to 3.0.

According to the present invention, it is possible to form the adhesive layer on the semiconductor wafer with a uniform film thickness and less waste of the adhesive, and further to avoid the bending of the semiconductor wafer due to the heating for the B stage of the adhesive layer, Provided are a method for producing a semiconductor wafer with an adhesive layer, a photosensitive adhesive used in such a manufacturing method, a semiconductor device having a semiconductor wafer that can be produced by such a manufacturing method, and a photosensitive adhesive for screen printing.

BRIEF DESCRIPTION OF THE DRAWINGS 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.
3 is a schematic diagram illustrating an embodiment of a method of manufacturing 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 cross section which shows one Embodiment of a semiconductor device.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of the manufacturing method of the semiconductor wafer with an adhesive bond layer, the photosensitive adhesive agent, a semiconductor device, and the screen printing photosensitive adhesive agent which concerns on this invention is described in detail, referring drawings. However, this invention is not limited to the following embodiment.

The manufacturing method of the semiconductor device which concerns on this embodiment is a process (photosensitive adhesive bond layer formation process) which apply | coats a photosensitive adhesive agent to the whole one surface of a semiconductor wafer by screen printing, and forms a photosensitive adhesive bond layer, and the photosensitive adhesive bond layer is used. It includes a step (B staged step) of forming a B stage by exposure, and a step (dicing step) of cutting the semiconductor wafer together with the B staged photosensitive adhesive layer.

(Photosensitive Adhesive Layer Forming Step)

The semiconductor wafer 6 shown in FIG. 1 is used for forming the 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. The circuit may already be formed in the semiconductor wafer 6 by a previous process. In the photosensitive adhesive layer formation process, for example, as shown in FIG. 1, the photosensitive adhesive agent 5 is apply | coated by the screen printing method to the surface (back surface) on the opposite side to the surface where the circuit of the semiconductor wafer 6 is formed. (Print). Thereby, the photosensitive adhesive bond layer 7 of uniform thickness is formed on the back surface of the semiconductor wafer 6 as shown in FIG.

Screen printing methods generally include the following two methods. One is the construction method using what is called a metal printing plate in which the opening part patterned to the flat metal plate was formed. In the above method, a metal printing plate is provided on an object to be printed, and ink is applied by rubbing the ink mounted on the metal printing plate with a metal plate called skid. By this process, ink is applied in the shape of an opening pattern formed on a metal printing plate.

As another screen printing method, there is a method using a so-called mesh printing plate embedded in a resin or the like, leaving only a portion to be coated in a mesh prepared by weaving a thread such as stainless steel, nylon and polyester. In the above method, the ink mounted on the mesh printing plate is rubbed with a resin or metal plate called a scraper. By this process, the ink penetrates into the openings not embedded in the resin of the mesh printing plate or the like. Next, the skid made of polyurethane, silicone rubber or the like is rubbed onto the mesh printing plate. By this process, the ink that has penetrated the openings is transferred onto the printing object to complete the printing process.

In this embodiment, since any printing method can selectively apply | coat an adhesive only to a desired position and area | region, waste of adhesive can be reduced and it is excellent in material yield.

When printing is to be performed in a relatively wide range in the method using a metal printing plate, since there is no integral member in the opening, the stress from the printing plate against the pressure of the skid in the opening does not occur. Therefore, the pressure concentrates in the center of the skid, the center of the skid is strongly pressed into the opening, and the film thickness of the photosensitive adhesive layer tends to decrease in the center of the opening. That is, in general, the wider the opening, the more strongly the center part of the skid is pressed, and the film thickness of the photosensitive adhesive layer in the center tends to decrease.

On the other hand, in the construction method using a mesh printing plate, since there is a mesh thread in an opening part, the stress from the mesh printing plate with respect to the pressure of a skid generate | occur | produces. That is, since the mesh chamber in the opening also functions as a supporting member in the skid center, the skid is not strongly pressed into the opening. For this reason, a film thickness does not fall also in a skid center part, and a uniform photosensitive adhesive bond layer can be obtained.

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

(B staged process)

The said photosensitive adhesive bond layer 7 is a photosensitive adhesive bond layer which has adhesiveness with respect to a to-be-adhered body after B-stage by exposure. On the applied photosensitive adhesive layer 7, the photosensitive adhesive agent 5 which comprises the photosensitive adhesive bond layer 7 is irradiated by B or ultraviolet-ray by an exposure apparatus. Thereby, the polymerization reaction by the photoinitiator and the radiation polymerizable compound contained in the photosensitive adhesive agent 5 advances, and the B-stage photosensitive adhesive bond layer 8 has suitable adhesiveness and adhesiveness. Specifically, the photosensitive adhesive bond layer 8 is fixed to the semiconductor wafer 6. Thus, by performing B stage formation of the photosensitive adhesive bond layer 7 by exposure instead of heating, application | coating of the photosensitive adhesive agent 5 and the photosensitive adhesive bond layer (with the back grind tape bonded to the semiconductor wafer 6) The B stage of 7) can be performed.

It is preferable to perform exposure in the state which laminated | stacked the transparent cover film in the photosensitive adhesive bond layer 7 under nitrogen atmosphere, under vacuum conditions, or a viewpoint from avoiding the inhibition of the photopolymerization reaction by oxygen. In more detail, the photosensitive adhesive bond layer 8 staged by exposure has the moderate adhesiveness which enables the individualization by dicing and peeling from the support body at the time of dicing, a semiconductor chip, and a glass substrate. It has adhesiveness to adherends, such as these. The detail of the photosensitive adhesive bond layer 8 which has such a function is mentioned later.

It can be confirmed that the photosensitive adhesive bond layer 8 B staged by the tag force (surface tag force) of the surface at 30 degreeC of the exposed photosensitive adhesive bond layer 8 being ²⁰⁰ gf / cm <^2> or less.

When surface tagging force in 30 degreeC exceeds ²⁰⁰ gf / cm < ² >, the adhesiveness of the surface at room temperature of the photosensitive adhesive bond layer 8 will become high, and there exists a tendency for handleability to fall. Moreover, peelability with the dicing film after dicing falls and there exists a tendency for pick-up property to fall. Moreover, when the surface tag force at 30 ° C is 1 gf / cm ² or less, the adhesiveness of the photosensitive adhesive becomes low, water penetrates into the interface between the photosensitive adhesive and the dicing film during dicing, and chip scattering tends to occur. have.

It is preferable that the surface tag force at 120 degreeC of the exposed photosensitive adhesive bond layer 8 is 200 gf / cm <^2> or more. If the surface tag force at 120 ° C. is less than ²⁰⁰ gf / cm ² , the thermal compressibility is impaired, and there is a tendency for voids to occur during thermocompression bonding or the thermocompression temperature becomes high. When the surface tag force at 120 ° C is 500 gf / cm ² or more, the photosensitive adhesive is excessively wet-diffused at the time of thermocompression, and the photosensitive adhesive tends to protrude on the chip side.

The said surface tag force is the value measured as follows. The photosensitive adhesive agent is apply | coated on a silicon wafer by the screen printing method, and it is 1000mJ / cm in nitrogen atmosphere by the high precision parallel exposure machine (Ok Seisakusho make, "EXM-1172-B-∞" (brand name)) to the obtained coating film. ² is exposed. Then, the photosensitive adhesive bond layer 8 at 30 degreeC and 120 degreeC on conditions of probe diameter 5.1mm, peeling speed 10mm / s, contact load 100gf / cm <^2> , contact time 1s using the probe tagging tester by Resca company (8) The tack force of the surface of) is measured. A parallel exposure machine ("ML-210FM mask aligner" (brand name)) can be used instead of the above-mentioned high precision parallel exposure machine.

Dicing Process

Next, the semiconductor wafer 11 with the adhesive layer which has the semiconductor wafer 6 and the photosensitive adhesive bond layer 8 formed on the back surface was diced from the wafer side, and the semiconductor chip 11 separated into pieces is produced (FIG. 4). In other words, the semiconductor wafer 6 is cut into a plurality of semiconductor chips 11 by cutting the semiconductor wafer 6 by a dicing machine. It is preferable that the dicing film 10 be affixed on the back surface of the semiconductor wafer 6 in which the said photosensitive adhesive bond layer 8 was formed before this dicing process. Affixing may be performed, heating as needed. For example, it is preferable to perform using the dicing blade 12 in the state which fixed the whole to the frame (wafer ring) 9 by the dicing film 10 (FIG. 4). The semiconductor chip 11 having the separated 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 arrange | positioned on the support member 14 prepared separately. Alternatively, a semiconductor chip 13b separate from the semiconductor chip 13a is disposed on the semiconductor chip 13a bonded to the support member 14 in advance. At this time, the photosensitive adhesive bond layers 16 and 17 are thermocompressed so that the semiconductor chip 13a, the support member 14, the semiconductor chip 13b, and the semiconductor chip 13a are adhered, and the semiconductor chips 13a and 13b are bonded. The silver is adhesively fixed to the support member 14 or the semiconductor chip 13a.

Thereafter, 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 together with the bonding wires 18 to the sealing material 15. By sealing, the semiconductor package (semiconductor device) as shown in FIG. 6 is completed.

According to the manufacturing method of the semiconductor device demonstrated above, the photosensitive adhesive agent 5 for bonding the semiconductor chip 13a, the support member 14, or the semiconductor chips 13a and 13b comrades is the semiconductor wafer 6 by screen printing. It is possible to apply only on). Thereby, application | coating to a desired film thickness is possible by a change of a printing plate irrespective of the composition of the photosensitive adhesive agent 5. Therefore, 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, preferable embodiment of the photosensitive adhesive agent which concerns on this embodiment is demonstrated. This photosensitive adhesive agent can be used suitably as the said photosensitive adhesive agent 5 in the manufacturing method of the semiconductor device mentioned above.

The photosensitive adhesive agent concerning this embodiment contains (A) thermosetting resin, (B) radiation polymeric compound, and (C) photoinitiator.

(A) A thermosetting resin will not be specifically limited if it is a component which consists of reactive compounds which generate | occur | produce a crosslinking reaction by heating, For example, an epoxy resin, a cyanate ester resin, a maleimide resin, allyl amideimide resin, a phenol resin, a 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, poly Isocyanate resin, resin containing tris (2-hydroxyethyl) isocyanurate, resin containing triallyl trimellitate, thermosetting resin synthesized from cyclopentadiene and thermosetting resin by trimerization of aromatic dicyanamid Can be mentioned. Especially, in combination with a polyimide resin, an epoxy resin, a maleimide resin, and an allyl amide imide resin are preferable at the point which can have the outstanding adhesive force at high temperature. In addition, these thermosetting resins can be used individually by 1 type or in combination of 2 or more types.

It is preferable that an epoxy resin contains at least 2 or more epoxy groups in a molecule | numerator, and the epoxy resin of the glycidyl ether type of a phenol is more preferable at the point of thermocompression property, curability, and hardened | cured material characteristic. Examples of such resins include bisphenol A (or AD, S and F) glycidyl ethers, hydrogenated bisphenol A glycidyl ethers, ethylene oxide adduct bisphenol A glycidyl ethers, and propylene. Oxide adduct bisphenol A glycidyl ether, glycidyl ether of phenol novolak resin, glycidyl ether of cresol novolak resin, glycidyl ether of bisphenol A novolak resin, glycidyl ether of naphthalene resin , Trifunctional (or tetrafunctional) glycidyl ether, glycidyl ether of dicyclopentadiene phenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) glycidylamine And glycidylamine of naphthalene resin. These may be used singly or in combination of two or more.

As an epoxy resin, the use of high purity products having reduced alkali metal ions, alkaline earth metal ions, halogen ions, especially chlorine ions or hydrolyzable chlorine, such as chlorine ions or hydrolysable chlorine to 300 ppm or less, is recommended from the viewpoint of preventing electro migration and corrosion of metal conductor circuits. desirable.

It is preferable that it is 10-80 mass% with respect to the photosensitive adhesive whole quantity, and, as for quantity of thermosetting resins, such as an epoxy resin, it is more preferable that it is 20-60 mass% from a viewpoint of the reliability of a photosensitive adhesive agent. When this amount exceeds 80 mass%, the viscosity of the photosensitive adhesive agent becomes high and there exists a tendency for printability to fall. On the other hand, when it is less than 10 mass%, there exists a tendency for sufficient thermocompression property and high temperature adhesiveness not to be obtained. 10 mass%, 20 mass%, 33 mass%, 42.5 mass%, 60 mass%, or 80 mass% may be sufficient as the upper limit and the lower limit of the quantity of a thermosetting resin with respect to the photosensitive adhesive whole quantity.

(A) It is preferable that 5% mass reduction temperature is 150 degreeC or more as a thermosetting resin, It is more preferable that it is 180 degreeC or more, It is still more preferable that it is 200 degreeC or more. Here, the 5% mass reduction temperature is measured under a temperature increase rate of 10 ° C./min and a nitrogen flow (400 mL / min) using a differential thermal thermogravimetry simultaneous measurement device (TG / DTA6300 manufactured by SII Nanotechnology) as a thermosetting resin. It is the 5% mass reduction temperature at the time of doing. By applying the thermosetting resin with a high 5% mass reduction temperature, volatilization of the thermosetting resin at the time of thermocompression bonding or thermosetting can be suppressed. Examples of the thermosetting resin having such heat resistance include epoxy resins having an aromatic ring in the molecule, and particularly from the viewpoint of adhesiveness and heat resistance, trifunctional (or tetrafunctional) glycidylamine and bisphenol A (or AD type) , S-type, F-type) glycidyl ether is preferably used.

It is preferable that the photosensitive adhesive agent concerning this embodiment contains a thermosetting initiator (hardening accelerator). The thermosetting initiator is not particularly limited as long as it is a compound that promotes curing or polymerization of the epoxy resin by heating, and examples thereof include phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, and alicyclic acids. 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, methacrylic acid 2- (0- [1'-methyl Propylideneamino] carboxyamino) ethyl, 1,8-diazabicyclo [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. Moreover, imidazole is especially preferable also from a viewpoint of adhesiveness, heat resistance, and storage stability. The upper limit and the 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 imidazole, it is preferable that reaction start temperature is 50 degreeC or more, It is more preferable that it is 80 degreeC or more, It is most preferable that it is 100 degreeC or more. Since the storage stability of the photosensitive adhesive agent will fall when reaction start temperature is less than 50 degreeC, there exists a tendency for the viscosity of a photosensitive adhesive agent to rise and it becomes difficult to control a film thickness.

As imidazole, Preferably, it is preferable to use the compound whose average particle diameter is 10 micrometers or less, More preferably, it is 8 micrometers or less, Most preferably, it is 5 micrometers or less. By using the imidazole of such average particle diameter, the viscosity change of the photosensitive adhesive agent can be suppressed, and sedimentation of imidazole can be suppressed. In addition, when a thin film of the photosensitive adhesive agent is formed, a uniform film can be obtained by reducing the surface irregularities. In addition, when hardening, since hardening of a photosensitive adhesive agent can be advanced uniformly, it is thought that the outgas can be reduced. In addition, good storage stability can be obtained by using an imidazole lacking solubility in an epoxy resin.

As imidazole, imidazole which melt | dissolves in an epoxy resin can also be used. By using such imidazoles, the unevenness | corrugation of the surface at the time of forming the thin film of the photosensitive adhesive agent can be reduced further. Examples of such imidazoles include, but are not limited to, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole. And 1-cyanoethyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole and the like.

The photosensitive adhesive may contain a phenolic compound as a curing agent. As a phenol type compound, the phenol type compound which has at least 2 or more phenolic hydroxyl group in a molecule | numerator is more preferable. As such a compound, For example, a phenol novolak, a cresol novolak, t-butyl phenol novolak, a dicyclopentadiene cresol novolak, a dicyclopentadiene phenol novolak, a xylylene modified phenol novolak, a naphthol type compound, Trisphenol type compounds, tetrakisphenol novolak, bisphenol A novolak, poly-p-vinylphenol, and a phenol aralkyl resin are mentioned. Among these, it is preferable that a number average molecular weight exists in the range of 400-4000. Thereby, the outgas at the time of heating which causes contamination of a semiconductor element, an apparatus, etc. at the time of the heating at the assembly of a semiconductor device can be suppressed. It is preferable that it is 50-120 mass parts with respect to 100 mass parts of thermosetting resins, and, as for the quantity of a phenol type compound, it is more preferable that it is 70-100 mass parts.

Examples of the (B) radiation polymerizable compound include compounds having an ethylenically unsaturated group, and examples of the ethylenically unsaturated group include vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide and nadyi. A mid group, a (meth) acryl group, etc. are mentioned. From a reactive viewpoint, a (meth) acryl group is preferable and it is preferable to contain monofunctional (meth) acrylate. By adding monofunctional (meth) acrylate, the crosslinking density of the photosensitive adhesive agent can be reduced, especially at the time of exposure for B stage formation, and it can be made the favorable state of thermocompression property after exposure, low stress, and adhesiveness. .

It is preferable that the 5% mass reduction temperature of monofunctional (meth) acrylate is 100 degreeC or more, It is more preferable that it is 120 degreeC or more, It is still more preferable that it is 150 degreeC or more, It is most preferable that it is 180 degreeC or more. Here, 5% mass reduction temperature is a monofunctional (meth) acrylate using a differential thermal thermogravimetry simultaneous measurement apparatus (SII nanotechnology company make: TG / DTA6300), temperature rising rate 10 ° C / min, nitrogen flow (400 ml) / min) is a 5% mass reduction temperature as measured under. By applying monofunctional (meth) acrylate having a high 5% mass reduction temperature, volatilization of unreacted monofunctional (meth) acrylate remaining after B-stage by exposure is suppressed during thermocompression or thermosetting. can do.

If it is such monofunctional (meth) acrylate, it will not specifically limit, Glycidyl group containing (meth) acrylate, phenol EO modified (meth) acrylate, phenol PO modified (meth) acrylate, nonylphenol EO modified (meth) Acrylate, nonylphenol PO modified (meth) acrylate, phenolic hydroxyl group-containing (meth) acrylate, hydroxyl group-containing (meth) acrylate, phenylphenol glycidyl ether (meth) acrylate and phenoxyethyl (meth) acrylic Aromatic (meth) acrylates, such as an acrylate, an imide group containing (meth) acrylate, a carboxyl group containing (meth) acrylate, isoboroyl containing (meth) acrylate, and dicyclopentadienyl group containing (meth) acrylate And isoboroyl (meth) acrylate can be used.

As monofunctional (meth) acrylate, it is preferable to have a urethane group, an isocyanuric group, an imide group, or a hydroxyl group from a viewpoint of adhesiveness with the to-be-adhered body after B stage formation, adhesiveness after hardening, and heat resistance, and especially imide group in a molecule | numerator It is preferable that it is monofunctional (meth) acrylate which has.

Monofunctional (meth) acrylate which has an epoxy group can also be used preferably. As monofunctional (meth) acrylate which has an epoxy group, it is preferable that a 5% mass reduction temperature is 150 degreeC or more from a viewpoint of storage stability, adhesiveness, low outgas resistance, heat resistance reliability, and moisture resistance reliability, and it is more preferable that it is 180 degreeC or more. It is most preferable that it is 200 degreeC or more. Although it does not specifically limit as monofunctional (meth) acrylate which has such an epoxy group, The said heat resistance can be satisfy | filled by using the polyfunctional epoxy resin whose 5% mass reduction 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, Glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl methacrylate In addition to glycidyl ether, the compound etc. which are obtained by making the compound which has a functional group and ethylenically unsaturated group which react with an epoxy group, and polyfunctional epoxy resin react are mentioned. Although it does not specifically limit as a functional group which reacts with the said epoxy group, Isocyanate group, a carboxyl group, phenolic hydroxyl group, a hydroxyl group, an acid anhydride, an amino group, a thiol group, an amide group, etc. are mentioned. These compounds may be used singly or in combination of two or more.

The monofunctional (meth) acrylate having an epoxy group is, for example, 0.1 to 1 equivalent of a polyfunctional epoxy resin having at least two or more epoxy groups in one molecule in the presence of triphenylphosphine or tetrabutylammonium bromide, and one equivalent of an epoxy group. It is obtained by reacting 0.9 equivalent of (meth) acrylic acid. Further, 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 by reacting a polyfunctional epoxy resin with an isocyanate group-containing (meth) acrylate Glycidyl group containing urethane (meth) acrylate etc. are obtained.

The monofunctional (meth) acrylate having an epoxy group has a 5% mass reduction temperature in terms of storage stability, adhesion, low heating gas resistance, heat resistance and moisture resistance of the package during assembling heating of the semiconductor device and after assembling the semiconductor device. It is preferable that it is 150 degreeC or more from the point which can suppress the volatilization by heat-drying at the time of adhesive film (photosensitive adhesive bond layer) formation, or segregation to the surface, and it is effective to reduce the space | gap by the outgas at the time of thermosetting, peeling, and adhesiveness fall. It is more preferable that it is 180 degreeC or more from the point which can be suppressed, It is still more preferable that it is 200 degreeC or more, It is most preferable that it is 260 degreeC or more from the point which can suppress the space | gap and peeling by volatilization of the unreacted component at the time of reflow. desirable. As monofunctional (meth) acrylate which has such an epoxy group, the compound which has an aromatic ring in a molecule | numerator is preferable.

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

Although it does not specifically limit as a monofunctional (meth) acrylate component which has an epoxy group which satisfy | fills the said heat resistance and purity, Bisphenol A type (or AD type, S type, F type) glycidyl ether, hydrogenated bisphenol A type glyc Cedyl ether, ethylene oxide adduct bisphenol A and / or F glycidyl ether, propylene oxide adduct bisphenol A and / or F glycidyl ether, glycidyl ether of phenol novolak resin, cresolno Glycidyl ether of volac resin, Glycidyl ether of bisphenol A novolak resin, Glycidyl ether of naphthalene resin, Glycidyl ether of trifunctional type (or tetrafunctional type), Glyc of dicyclopentadiene phenol resin The thing which used as a raw material the cylyl ether, the glycidyl ester of dimer acid, the trifunctional (or tetrafunctional) glycidylamine, and the glycidylamine of naphthalene resin etc. is mentioned.

In particular, in order to improve thermocompressability, low stress and adhesion, the number of epoxy groups and ethylenically unsaturated groups is preferably 3 or less, and particularly preferably the number of ethylenically unsaturated groups is 2 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 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, and R ¹⁵ , R ¹⁷ and R ¹⁸ represents an organic group having an epoxy group or an ethylenically unsaturated group. f represents an integer. f is 1-10, for example.

It is preferable that the quantity of the said monofunctional (meth) acrylate is 20-100 mass% with respect to the (B) radiation polymeric compound, It is more preferable that it is 40-100 mass%, It is most preferable that it is 50-100 mass%. . By making monofunctional (meth) acrylate the quantity mentioned above, adhesiveness with the to-be-adhered body after B stage formation and thermocompression property can be improved.

(B) As a radiation polymeric compound, you may contain the bifunctional or more (meth) acrylate. Although there is no restriction | limiting in particular as such an acrylate, Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol Dimethacrylate, trimethylolpropanediacrylate, trimethylolpropanetriacrylate, trimethylolpropanedimethacrylate, trimethylolpropanetrimethacrylate, 1,4-butanedioldiacrylate, 1,6-hexanediol Diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol Tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythr Tolhexamethacrylate, 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 Triacrylate of -hydroxyethyl) isocyanurate, the compound represented by following formula (6), urethane acrylate, urethane methacrylate, urea acrylate, etc. are mentioned.

In said Formula (6), R <^19> and R <^20> represents a hydrogen atom or a methyl group each independently, and g and h each independently represent the integer of 1-20.

These radiation polymerizable compounds can be used individually by 1 type or in combination of 2 or more types. Especially, the radiation polymeric compound which has a glycol skeleton represented by the said General formula (6) can fully provide the solvent resistance after hardening, and is preferable at the point which has a high viscosity 5% mass reduction temperature with low viscosity.

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 to suppress the warpage of the semiconductor wafer (lower warpage). It is preferable that a polymerization functional group equivalent is 200 eq / g or more, it is more preferable that it is 300 eq / g or more, and, as for the radiation polymeric compound with high functional group equivalent, it is most preferable that it is 400 eq / g or more. By using the radiation polymerizable compound which has an ether skeleton, urethane group, and / or isocyanuric group whose polymerization functional group equivalent is 200 eq / g or more, it becomes possible to improve the adhesiveness of a photosensitive adhesive agent, and to make it low stress and low deflection. The radiation polymerizable compound whose polymerization functional group equivalent is 200 eq / g or more, and the radiation polymerizable compound whose polymerization functional group equivalent is less than 200 eq / g can also be used together.

(B) It is preferable that the quantity of a radiation polymeric compound is 10-95 mass% with respect to the photosensitive adhesive whole quantity, It is more preferable that it is 20-90 mass% from the viewpoint of the wet expandability at the time of chip bonding, and shape retention after B stage formation It is most preferable that it is 40-90 mass% from a viewpoint. If the component (B) is less than 10% by mass, the tag force after B stage formation tends to be large, and if it exceeds 95% by mass, the adhesive strength after thermosetting tends to decrease. 10 mass%, 20 mass%, 40 mass%, 56.7 mass%, 66 mass%, 90 mass%, or 95 mass% may be sufficient as the upper limit and the lower limit of the quantity of a radiation polymeric compound with respect to the photosensitive adhesive whole quantity.

(B) The radiation polymerizable compound is preferably liquid at room temperature (15 ° C. to 30 ° C.), and in view of the omission of the photosensitive adhesive from the mesh printing plate, the viscosity is preferably 5000 mPa · s or less, and the magnetic flux after printing In consideration of further flattening, it is more preferably 3000 mPa · s or less. When viscosity exceeds 5000 mPa * s, the viscosity of a photosensitive adhesive agent rises and there exists a tendency for printability to fall.

(B) It is preferable that 5% mass reduction temperature is 120 degreeC or more as a radiation polymeric compound, It is more preferable that it is 150 degreeC or more, It is still more preferable that it is 180 degreeC or more. Here, the 5% mass reduction temperature means a temperature increase rate of 10 ° C./min and a nitrogen flow (400 ml / min) using a differential thermal thermogravimetry simultaneous measurement device (SII Nanotechnology Co., Ltd .: TG / DTA6300). It is a 5% mass reduction temperature when measured under. By applying the radiation polymeric compound with a high 5% mass reduction temperature, volatilization at the time of thermocompression bonding or thermosetting can be suppressed.

(C) As a photoinitiator (photoinitiator), it is preferable that the molecular extinction coefficient with respect to the light of wavelength 365nm is 100 ml / g * cm or more, and it is more preferable that it is 200 ml / g * cm or more from the point of the photopolymerization sensitivity improvement. In addition, a molecular extinction coefficient is calculated | required by preparing 0.001 mass% acetonitrile solution of a sample, and measuring the absorbance with this solution using a spectrophotometer (The Hitachi High-Technologies company make, "U-3310" (brand name)). .

As such a component (C), for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane- 1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1,2,4-diethylthioke Aromatic ketones such as santone, 2-ethylanthraquinone and phenanthrenequinone, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, and 2- (o- Chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl ) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5 2,4,5-triarylimidazole dimer, 9-phenyl, such as -phenylimidazole dimer and 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer Acridine derivatives such as acridine and 1,7-bis (9,9'-acridinyl) heptane Bisacylphosphine oxides such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and bis (2,4,6, -trimethylbenzoyl) -phenylphosphine oxide; and The compound which has maleimide, etc. are mentioned. These may be used singly or in combination of two or more.

2,2-dimethoxy-1,2-diphenylethan-1-one and 2-benzyl-2-dimethylamino-1- (4-in terms of solubility in a photosensitive adhesive agent containing no solvent among the photopolymerization initiators described above Morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethan-1-one and 2-methyl-1- (4- (methylthio) phenyl) -2-morpholi Nopropan-1-one is preferably used. In addition, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethon in that the B-staging of the photosensitive adhesive layer can be achieved by exposure even under an air atmosphere. Toxy-1,2-diphenylethan-1-one and 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one are preferably used.

(C) component may also contain the photoinitiator which expresses the function which promotes superposition | polymerization and / or reaction of an epoxy resin by irradiation of a radiation. As such a photoinitiator, the photobase generator which generate | occur | produces a base by irradiation, the photoacid generator which generate | occur | produce an acid by irradiation, etc. are mentioned, for example, A photobase generator is especially preferable.

By using a photobase generator, the adhesiveness (high temperature adhesiveness) and moisture resistance at the high temperature of a photosensitive adhesive agent to a to-be-adhered body can further be improved. The reason for this is that the base generated from the photobase generator effectively acts as a curing catalyst for the epoxy resin, so that the crosslinking density can be further increased, and the resulting curing catalyst rarely corrodes the substrate or the like. . By containing a photobase generator in a photosensitive adhesive agent, a crosslinking density can be improved and the outgas at the time of high temperature standing can be reduced more. Moreover, it is thought that the temperature of a hardening process can be made low temperature and short time.

The photobase generator can be used without particular limitation as long as it is a compound that generates a base during irradiation. As a base to generate | occur | produce, a strong basic compound is preferable at the point of reactivity and hardening rate.

As a base which arises at the time of such irradiation, imidazole derivatives, such as imidazole, 2, 4- dimethyl imidazole, and 1-methyl imidazole, piper, such as piperazine and 2, 5- dimethyl piperazine, for example. Piperidine derivatives such as razine derivatives, piperidine and 1,2-dimethylpiperidine, proline derivatives, trialkylamine derivatives such as trimethylamine, triethylamine and triethanolamine, 4-methylaminopyridine and 4-dimethyl Pyridine derivatives substituted with amino or alkylamino groups at 4 positions such as aminopyridine, pyrrolidine derivatives such as pyrrolidine and n-methylpyrrolidine, dihydropyridine derivatives, triethylenediamine and 1,8-diazabiscyclo Alicyclic amine derivatives such as (5,4,0) undecene-1 (DBU) and benzylamine derivatives such as benzylmethylamine, benzyldimethylamine and benzyldiethylamine.

As a photobase generator which generates such a base by irradiation with radiation, for example, Journal of Photopolymer Science and Technology 12, 313-314 (1999) or Chemistry of Materials 11, 170 To 176 (1999)], etc. can be used quaternary ammonium salt derivatives. Since these produce | generate high basic trialkylamine by irradiation of actinic light (radiation), they are optimal for hardening of an epoxy resin.

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

Examples of the photobase generator that generates a base by irradiation of active light include 2,4-dimethoxy-1,2-diphenylethan-1-one, 1,2-octanedione, and 1- [4- (phenylthio) -2- (o-benzoyloxime)], ethanone and 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 commercially available as an oxime derivative or an optical radical generator -1-one, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) -Butanone-1, hexaarylbisimidazole derivatives (substituents such as halogen, alkoxy group, nitro group and cyano group may be substituted with phenyl group), benzoisoxazolone derivatives and the like can be used.

As a photobase generator, the compound which introduce | transduced the group which generate | occur | produces a base in the main chain and / or side chain of a polymer can also be used. As molecular weight in this case, the weight average molecular weights 1000-100000 are preferable from a viewpoint of adhesiveness, fluidity | liquidity, and heat resistance as a photosensitive adhesive agent, and it is more preferable that it is 5000-30000.

Since the photobase generator does not exhibit reactivity with the epoxy resin in the unexposed state, the photobase generator is excellent in storage stability at room temperature.

The quantity of a photoinitiator may be 5 mass parts or more or 1 mass part or more with respect to 100 mass parts of radiation polymeric compounds. The quantity of a photoinitiator may be 0.1 mass part or less or 1 mass part or less with respect to 100 mass parts of radiation polymeric compounds.

The photosensitive adhesive agent concerning this embodiment can use a sensitizer together as needed. Examples of the sensitizer include camphorquinone, benzyl, diacetyl, benzyl dimethyl 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-isopropyl thioxanthone, 2-nitro thioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxide Santone, 2-chloro-7-trifluoromethyl thioxanthone, thioxanthone-10,10-oxide, thioxanthone-10-oxide, benzoin methyl ether, benzoin ethyl ether, isopropyl ether, The compound containing a benzoin isobutyl ether, benzophenone, bis (4-dimethylaminophenyl) ketone, 4,4'-bisdiethylamino benzophenone, and an azide group is mentioned. These can be used individually by 1 type or in combination of 2 or more types.

In the photosensitive adhesive agent which concerns on this embodiment, it can also contain (D) thermoplastic resin from the point which improves low stress, adhesiveness with a to-be-adhered body, and thermocompression bonding. It is preferable that the glass transition temperature (Tg) of (D) component is 150 degrees C or less, It is more preferable that it is 120 degrees C or less, It is still more preferable that it is 100 degrees C or less, It is most preferable that it is 80 degrees C or less. When this Tg exceeds 150 degreeC, there exists a tendency for the viscosity of a photosensitive adhesive agent to rise. Moreover, when thermocompression bonding with a to-be-adhered body, high temperature of 150 degreeC or more is required, and there exists a tendency for a warpage to arise easily in a semiconductor wafer.

Here, "Tg" means the main dispersion peak temperature of the filmed (D) component. Using a viscoelastic analyzer "RSA-2" (trade name) manufactured by Leometrics, the film thickness was measured under conditions of 100 µm, a heating rate of 5 ° C / min, a frequency of 1 Hz, and a measurement temperature of -150 to 300 ° C. The tanδ peak temperature observed in the vicinity is the main dispersion peak temperature.

It is preferable to control the weight average molecular weight of (D) component in the range of 5000-50000, and it is more preferable that it is 10000-30000 in the point which can make highly compatible thermocompression bonding and high temperature adhesiveness. Here, a "weight average molecular weight" means the weight average molecular weight when it measured by polystyrene conversion using high performance liquid chromatography "C-R4A" (brand name) 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 In addition to resins, polyesterimide resins, copolymers thereof, and precursors thereof (polyamic acid, etc.), polybenzoxazole resins, phenoxy resins, polysulfone resins, polyethersulfone resins, polyphenylene sulfide resins, polyesters Resins, polyether resins, polycarbonate resins, polyether ketone resins, (meth) acrylic copolymers having a weight average molecular weight of 10,000 to 1 million, novolak resins and phenol resins. These may be used singly or in combination of two or more. Furthermore, glycol groups, such as ethylene glycol and propylene glycol, carboxyl group and / or hydroxyl group, may be provided to the principal chain and / or side chain of these resin.

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. For example, a polyimide resin can be obtained by condensation reaction of tetracarboxylic dianhydride and diamine by a well-known method. That is, the sum of the diamines is preferably 0.5 to 2.0 moles, more preferably 0.8 to moles of tetracarboxylic dianhydride and diamine in an organic solvent in equimolar or 1.0 moles of tetracarboxylic dianhydride as necessary. The composition ratio is adjusted in the range of 1.0 mol (addition order of each component is arbitrary) and the addition reaction is carried out 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 rises to produce polyamic acid, which is a precursor of the polyimide resin. Moreover, in order to suppress the fall of the various characteristics of the photosensitive adhesive agent, it is preferable that the said tetracarboxylic dianhydride performed the refinement | purification process by recrystallization with acetic anhydride.

About the composition ratio of tetracarboxylic dianhydride and diamine in the said condensation reaction, when the sum total of diamine exceeds 2.0 mol with respect to a total of 1.0 mol of tetracarboxylic dianhydride, the polyimide which has an amine terminal in the obtained polyimide resin The amount of oligomer tends to increase. Moreover, the weight average molecular weight of a polyimide resin becomes low, and there exists a tendency for the various characteristics including the heat resistance of a photosensitive adhesive agent to become insufficient. On the other hand, when the sum total of diamine is less than 0.5 mol with respect to 1.0 mol total of tetracarboxylic dianhydride, there exists a tendency for the quantity of the polyimide resin oligomer which has an acid terminal (carboxyl terminal) to increase. Moreover, the weight average molecular weight of a polyimide resin becomes low, and there exists a tendency for the various characteristics including the heat resistance of a photosensitive adhesive agent to become insufficient.

The polyimide resin can be obtained by dehydrating and closing the reaction product (polyamic acid). The dehydration ring closure can be carried out by a thermal ring closure method for heat treatment, 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 polyimide resin, For example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, 2, 2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Dianhydrides, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydrides, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydrides, bis (2,3-dicarboxyphenyl) methane Dianhydrides, bis (3,4-dicarboxyphenyl) methane dianhydrides, bis (3,4-dicarboxyphenyl) sulfone dianhydrides, 3,4,9,10-perylenetetracarboxylic dianhydrides, bis ( 3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride, 2, 3,2 ', 3'-benzophenonetetracarboxylic dianhydride, 3,3,3', 4'-benzo Nontetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetra Carboxylic acid dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene -1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8, 9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3, 3 ', 4'-biphenyltetracarboxylic dianhydride, 3,4,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,2 ', 3'-biphenyltetracarboxylic acid Dianhydrides, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydrides, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydrides, non (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 (trimelitate anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride Water, 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 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) Nil] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane Dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydrides, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimelitic anhydride) , 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimelitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1 And 2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride and tetracarboxylic dianhydride represented by the following general formula (7). In the following general formula (7), a represents an integer of 2 to 20.

The tetracarboxylic dianhydride represented by the above formula (7) can be synthesized, for example, from trimellitic anhydride monochloride and the corresponding diol. Specifically, 1,2- (ethylene) bis (trimelitate anhydride), 1,3- (trimethylene) bis (trimelitate anhydride), 1,4- (tetramethylene) bis (trimelitate anhydride), 1,5- (pentamethylene) bis (trimelitate anhydride), 1,6- (hexamethylene) bis (trimelitate anhydride), 1,7- (heptamethylene) bis (trimelitate anhydride), 1, 8- (octamethylene) bis (trimethate anhydride), 1,9- (nonmethylene) bis (trimelitate anhydride), 1,10- (decamethylene) bis (trimelitate anhydride), 1,12- (Dodecamethylene) bis (trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimelitate anhydride), and 1,18- (octadecamethylene) bis (trimelitate anhydride) are mentioned. .

As tetracarboxylic dianhydride, the tetracarboxylic dianhydride represented by following formula (8) or (9) is preferable from a viewpoint of providing favorable solubility and moisture resistance to a solvent, and transparency to the light of wavelength 365nm. .

Such tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

(D) component can also use a carboxyl group and / or a phenolic hydroxyl group containing polyimide resin from a point which raises adhesive strength. It is preferable that the diamine used as a raw material of the said carboxyl group and / or the hydroxyl group containing polyimide resin contains aromatic diamine represented by 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'- diamino diphenyl ether, 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-dia Minodiphenylmethane, 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'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone , 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3, 3'-diaminodiphenylketone, 3,4'-diaminodiphenylketone, 4,4'-diaminodiphenylketone, 2,2-bis (3-ami Nophenyl) propane, 2,2 '-(3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoro Propane, 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-aminoenoxy) phenyl) sulfone, bis (4- (4-aminoenoxy) phenyl) sulfone, 3,3'-dihydroxy Aromatic diamines such as -4,4'-diaminobiphenyl and 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane, Aliphatic etherdiamine represented by the following general formula (14), and siloxane diamine represented by the following general formula (15) are mentioned.

Among the diamines, aliphatic ether diamines represented by the following general formula (14) are preferable in terms of providing compatibility with other components, and ethylene glycol and / or propylene glycol diamines are more preferable. In 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-148, manufactured by Sun Techno Chemical. And aliphatic diamines such as polyoxyalkylenediamines such as polyetheramines D-230, D-400, and D-2000 manufactured by BASF Corporation. It is preferable that these diamine is 20 mol% or more of all the diamine, and it is highly compatible with other compounding components, such as (A) thermosetting resin and (B) radiation polymerizable compound, and can be highly compatible with thermocompression bonding and high temperature adhesiveness. It is more preferable that it is 50 mol% or more from a point.

As said diamine, the siloxane diamine represented by following General formula (15) is preferable at the point which provides adhesiveness and adhesiveness at room temperature. In 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 represent 1 carbon. An alkyl group, a phenyl group, or a phenoxy group of 5 is represented, d shows the integer of 1-5.

It is preferable to make these diamine into 0.5-80 mol% of all diamine, and it is more preferable to set it as 1-50 mol% from the point which can be made highly compatible with thermocompression bonding and high temperature adhesiveness. When it is less than 0.5 mol%, the effect which added siloxane diamine becomes small, and when it exceeds 80 mol%, there exists a tendency for compatibility with other components and high temperature adhesiveness to fall.

As siloxane diamine represented by the said General formula (15), 1,1,3,3- tetramethyl- 1, 3-bis (4-aminophenyl) disiloxane as d in Formula (15) is 1 specifically, 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. 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, and 1,1,5,5-tetraphenyl- as d in Formula (15) is 2 3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) tri Siloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimeth Oxy-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 and 1,1,3,3,5,5- Hexapropyl-1,5-bis (3-aminopropyl) trisiloxane and the like.

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 preferable to design the Tg of the polyimide resin to be 150 ° C. or lower, and use the aliphatic ether diamine represented by the formula (14) as a diamine as a raw material of the polyimide resin. Is particularly preferred.

At the time of the synthesis of the polyimide resin, a monofunctional acid anhydride and / or a monofunctional amine, such as a compound represented by the following formulas (16), (17) or (18), is added to the condensation reaction solution, whereby Functional groups other than anhydride or diamine can be introduced. Moreover, the molecular weight of a polymer can be lowered by this, the viscosity of a photosensitive adhesive agent can be reduced, and thermocompression property can be improved.

The functional group (D) component which has a function which accelerates hardening of epoxy resins, such as imidazole, may have as a main chain and / or a side chain. For example, the imidazole containing polyimide can be obtained as follows. As a diamine component shown above, one part can be obtained using the imidazole group containing diamine represented by the following structural formula.

Since the polyimide resin can be uniformly B-stage, it is preferable that the transmittance of light having a wavelength of 365 nm when the thickness is molded to 30 μm is 10% or more, and in that it can be B-stage at a lower exposure dose. It is more preferable that it is 20% or more. Such a polyimide resin can be synthesized by, for example, reacting an acid anhydride represented by the general formula (7) with an aliphatic etherdiamine represented by the general formula (14) and / or a siloxanediamine represented by the general formula (15). Can be.

(D) It is preferable to use liquid liquid thermoplastic resin at normal temperature (25 degreeC) from the point which suppresses a raise of a viscosity and reduces the melt | dissolution residual in a photosensitive adhesive agent as (D) thermoplastic resin. Such a thermoplastic resin can be heated and reacted without using a solvent. In the photosensitive adhesive which does not apply the solvent as in the present embodiment, the process of solvent removal, reduction of remaining solvent, and reprecipitation process are reduced. useful. In addition, the liquid thermoplastic resin can be easily taken out from the reaction furnace. Although it does not specifically limit as such a liquid thermoplastic resin, Rubber-like polymers, such as a polybutadiene, an acrylonitrile butadiene oligomer, a polyisoprene and a polybutene, a polyolefin, an acrylic polymer, a silicone polymer, a polyurethane, a polyimide, a polyamideimide, etc. Can be mentioned. Especially, polyimide resin is used preferably.

As a liquid polyimide resin, it is obtained, for example by making the said acid anhydride react with aliphatic ether diamine and siloxane diamine. As a synthesis | combining method, it is obtained by disperse | distributing and heating an acid anhydride in aliphatic ether diamine and siloxane diamine, without adding a solvent.

The photosensitive adhesive agent concerning this embodiment has the minimum melt viscosity in 20 degreeC-300 degreeC, after exposing using a high precision parallel exposure machine (Ok Seisakusho make, "EXM-1172-B-∞" (brand name)). It is preferable that it is a photosensitive adhesive agent which is 30000 Pa * s or less. A parallel exposure machine ("ML-210FM mask aligner" (brand name)) can be used instead of the above-mentioned high precision parallel exposure machine.

In this specification, "minimum melt viscosity" is 20 degreeC when the sample after exposing with the light amount of 1000mJ / cm <^2> was measured using the viscoelasticity measuring apparatus ARES (made by EOMETICS Scientific FE Co., Ltd.). The minimum value of melt viscosity in -300 degreeC is shown. In addition, the measurement plate uses the parallel plate of diameter 8mm. The temperature increase rate is 5 ° C / min, the measurement temperature is 20 ° C to 300 ° C, and the frequency is measured condition of 1 Hz.

It is preferable that the said minimum melt viscosity is 20000 Pa * s or less, It is more preferable that it is 18000 Pa * s or less, It is still more preferable that it is 15000 Pa * s or less. By having the minimum melt viscosity in the said range, sufficient low temperature thermocompression property can be ensured and favorable adhesiveness can also be provided also to the board | substrate with an unevenness | corrugation. Although the minimum of the said minimum melt viscosity does not set in particular, It is preferable that it is 10 Pa * s or more from a viewpoint of handleability.

The thermal radical generating agent can be used for the photosensitive adhesive agent concerning this embodiment as needed. It is preferable that it is an organic peroxide as a thermal radical generating agent. The organic peroxide preferably has a half-life temperature of 80 ° C or higher for one minute, more preferably 100 ° C or higher, and most preferably 120 ° C or higher. The organic peroxide is selected in consideration of the production conditions of the photosensitive adhesive, film forming temperature, curing (bonding) conditions, other processing conditions, storage stability, and the like. Although it does not specifically limit as an organic peroxide which can be used, For example, 2, 5- dimethyl- 2, 5- di (t-butyl peroxy hexane), dicumyl peroxide, t-butyl peroxy-2-ethyl hexanate , t-hexyl peroxy-2-ethylhexanate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3 And 3,5-trimethylcyclohexane and bis (4-t-butylcyclohexyl) peroxydicarbonate. One of these may be used alone or in combination of two or more thereof. By containing an organic peroxide, the unreacted radiation polymerizable compound remaining after exposure can be made to react, and the reduction of outgas (low out gasification) and high adhesion can be attained.

0.01-20 mass% is preferable with respect to the whole quantity of a radiation polymerizable compound, 0.1-10 mass% is more preferable, and, as for the quantity of a thermal radical generating agent, 0.5-5 mass% is the most preferable. When it is less than 0.01 mass%, sclerosis | hardenability falls and the effect by addition becomes small, and when it exceeds 5 mass%, there exists a tendency which the increase of outgas amount and the fall of storage stability are seen.

The thermal radical generator is not particularly limited as long as it has a compound having a half-life temperature of 80 ° C. or higher for 1 minute. Hexane) (1 minute half-life temperature: 180 ° C), Percumyl D (manufactured by Nichiyu Co., Ltd.), and dicumylperoxide (1 minute half-life temperature: 175 ° C).

In the photosensitive adhesive according to the present embodiment, polymerization inhibitors or antioxidants such as quinones, polyhydric phenols, phenols, phosphites and sulfurs are not impaired in the curability of the photosensitive adhesive agent in order to impart storage stability, process adaptability or antioxidant properties. You may add more in the range which does not.

In addition, the photosensitive adhesive agent concerning this embodiment can also be made to contain a filler suitably. 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, aluminum oxide, and nitriding. Inorganic fillers such as aluminum, crystalline silica, amorphous silica, boron nitride, titania, glass, iron oxide and ceramics, and organic fillers such as carbon and rubber fillers, and can be used without particular limitation. have.

The filler can be used separately according to the desired function. For example, metal fillers are added for the purpose of imparting conductivity, thermal conductivity, thixotropy and the like to the photosensitive adhesive. The nonmetallic 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 added for the purpose of imparting toughness and the like to the photosensitive adhesive layer.

These metal fillers, inorganic fillers or organic fillers can be used individually by 1 type or in combination of 2 or more types. Especially, a metal filler or an inorganic filler is preferable at the point which can provide the electroconductivity, thermal conductivity, or low moisture absorption characteristic required for the adhesive material for semiconductor devices, and an insulating filler is preferable at the point which can provide insulation. Among the inorganic fillers or the insulating fillers, silica fillers are more preferable in terms of good dispersibility to the photosensitive adhesive and imparting high adhesion at the time of heat.

It is preferable that the said filler has an average particle diameter of 10 micrometers or less and a maximum particle diameter of 30 micrometers or less, It is more preferable that an average particle diameter is 5 micrometers or less and a maximum particle diameter is 20 micrometers or less. If the average particle diameter exceeds 10 µm and the maximum particle diameter exceeds 30 µm, there is a tendency that the effect of improving fracture toughness is not sufficiently obtained. The lower limit of the average particle size and the maximum particle size is not particularly limited, but is usually 0.001 µm or more.

Although the quantity of the said filler is determined by 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, 1-40 mass% is more preferable, 30 mass% is more preferable. By increasing the filler, low alpha, low moisture absorption, high elastic modulus can be achieved, and dicing property (cutting property by dicer blades), wire bonding property (ultrasound efficiency), and adhesive strength at heat can be effectively improved.

If the filler is increased more than necessary, the viscosity of the photosensitive adhesive tends to increase or the thermocompression 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 to balance the required properties. Mixing and kneading | mixing in the case of using a filler can be performed combining suitably dispersers, such as a normal stirrer, a grinder, a triaxial roll, and a ball mill, suitably.

Various coupling agents can also be added to the photosensitive adhesive agent which concerns on this embodiment in order to improve the interfacial bond between different materials. As a coupling agent, a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent are mentioned, for example. Especially, a silane coupling agent is preferable at the point which has a high effect, and the compound which has thermosetting functional groups, such as an epoxy group, and radiation polymerizable functional groups, such as methacrylate and / or acrylate, is more preferable. It is preferable that the boiling point and / or decomposition temperature of the said silane coupling agent are 150 degreeC or more, It is more preferable that it is 180 degreeC or more, It is still more preferable that it is 200 degreeC or more. That is, the silane coupling agent which has a boiling point and / or decomposition temperature of 200 degreeC or more, and has a thermosetting functional group, such as an epoxy group, and a radiation polymerizable functional group, such as methacrylate and / or acrylate, is the most preferable. It is preferable that the quantity of the said coupling agent shall be 0.01-20 mass parts with respect to 100 mass parts of photosensitive adhesive agents used from the surface of the effect, heat resistance, and cost.

An ion trapping agent may be further added to the photosensitive adhesive agent of this embodiment in order to adsorb | suck an ionic impurity and to improve insulation reliability at the time of moisture absorption. There is no restriction | limiting in particular as such an ion trapping agent, For example, the compound known as an anti-inflammatory agent for preventing copper from ionizing and eluting, such as a triazine thiol compound and a phenolic reducing agent, a powdery bismuth type, an antimony type, magnesium type And inorganic compounds such as aluminum, zirconium, calcium, titanium, tin and mixtures thereof. Although it does not specifically limit as a specific example, Toagosei Co., Ltd. inorganic ion trapping agent, brand names IXE-300 (antimony system), IXE-500 (bismuth system), IXE-600 (antimony, bismuth mixed system), IXE- 700 (magnesium, aluminum mixed system), IXE-800 (zirconium system), IXE-1100 (calcium system), and the like. These can be used individually by 1 type or in mixture of 2 or more types. As for the quantity of the said ion trapping agent, 0.01-10 mass parts is preferable with respect to 100 mass parts of photosensitive adhesive agents from an effect, heat resistance, cost, etc. by addition.

From the point of view of stably supplying the photosensitive adhesive to the opening of the mesh printing plate before printing, in view of the omission of the photosensitive adhesive from the mesh opening at printing, and the printing of the bubbles and the trace of the mesh of the photosensitive adhesive layer after printing From the viewpoint of flattening by spontaneously flowing the adhesive, the thixotropy index of the photosensitive adhesive is preferably 1.0 to 3.0. When the thixotropy index is 1.0 or more, it tends to be able to suppress the occurrence of sagging in the photosensitive adhesive supplied and applied by the printing method and to maintain a good print shape. Moreover, when this thixotropy index is 3.0 or less, there exists a tendency which can suppress generation | occurrence | production of the "lack", a scratch, etc. in the said photosensitive adhesive agent supplied and apply | coated by the printing method. The upper and lower limits of the thixotropic 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 in terms of handling the photosensitive adhesive such as supplying the photosensitive adhesive on the printing plate at the time of operation, in view of the omission of the photosensitive adhesive from the mesh opening at printing, and the photosensitive after printing. It is preferable that it is 1-100 Pa.s from a viewpoint of planarizing the bubble of the adhesive bond layer, or the trace of a mesh by the spontaneous flow of the photosensitive adhesive agent. The upper limit and the lower limit of the viscosity at 25 ° C. of the photosensitive adhesive agent may be 1 Pa.s, 8.5 Pa.s, 12.8 Pa.s, 16.0 Pa.s or 100 Pa.s.

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

<Examples>

Hereinafter, the present invention will be described in more detail by way of examples. However, this invention is not limited by the following example.

(Production of Photosensitive Adhesive)

First, the thermosetting resin and the radiation polymerizable compound were dissolved in a four-neck separable flask provided in an oil bath by heating to 60 ° C. under a nitrogen atmosphere. The thermosetting initiator and the photoinitiator were respectively added to the obtained solution, put into a grinder, and kneaded, and the degassing kneading was further performed for 1 hour at 5 Torr or less. Subsequently, the viscosity was adjusted by adding the radiation polymerizable compound and degassing kneading, and the photosensitive adhesive agent of the ratio which each component shows in Table 1 was obtained. The viscosity and thixotropy index in 25 degreeC of each photosensitive adhesive agent are as shown in Table 1.

(Formation of Photosensitive Adhesive Layer)

Using the MK-838SV printing machine (manufactured by Minami Corporation) with a V-screen V160 mesh printing plate (manufactured by NBC Mesh Tech Co., Ltd.), the obtained photosensitive adhesive was fabricated in a silicon wafer having a size of 8 inches φ and a thickness of 50 µm. Printing application | coating was performed in the circular shape of 6 inch (phi) on the back surface. When the state of the photosensitive adhesive agent after printing was visually confirmed, it was possible to form a uniform photosensitive adhesive layer without a scratch etc.

(Tack force measurement of the surface of the photosensitive adhesive bond layer after B-stage)

1000 mJ under a nitrogen atmosphere using a parallel exposure machine ("ML-210FM Mask Aligner" (brand name)) manufactured on the photosensitive adhesive bond layer formed on the silicon wafer by the screen printing method as Examples 1-4. It exposed at / cm <^2> and made the photosensitive adhesive bond layer B-stage. Next, as a comparative example 1, the silicon wafer which printed the photosensitive adhesive agent similar to Example 1 was prepared, it put in the drier at 100 degreeC for 1 hour, and B stage formation by heating was performed. After B staged, the surface tag of the photosensitive adhesive bond layer at 30 degreeC was carried out on condition of probe diameter 5.1mm, peeling speed 10mm / s, contact load 100gf / cm <^2> , contact time 1s using the probe tagging tester by Resca company. Force was measured. The surface tag force after B stage formation is as showing in Table 1.

(Observation of Warp of Silicon Wafer After B-Stage)

As a result of observing the silicon wafer after B-stage obtained by the said "Measurement of tack force of the surface of the photosensitive adhesive bond layer after B-stage formation", the silicon wafer in which the photosensitive adhesive bond layer obtained in Examples 1-4 was formed was not seen to bend. However, in the silicon wafer in which the photosensitive adhesive bond layer formed in the comparative example 1 was formed, the bending of the silicon wafer with the heating was seen, and the height difference of the edge part and center part of the silicon wafer was about 1.5 cm. The observation result of the bending of the silicon wafer after B stage formation is as Table 1 showing.

(Pick up)

After laminating a dicing tape on the silicon wafer side of the silicon wafer on which the photosensitive adhesive bond layer was formed by the screen printing method, and attaching it to the wafer ring, a dicing apparatus (DAD-3220 (brand name) manufactured by Disco Co., Ltd.) was used. Dicing was carried out using a 10 × 10 mm angle. In Examples 1 to 4, when the state of the silicon wafer after dicing was confirmed, dicing was possible without the lack of a silicon chip. Moreover, when 10 silicon chips were picked up from the dicing tape, there was no transfer of the photosensitive adhesive agent to the dicing tape, and pick-up property was also favorable. On the other hand, in the comparative example 1, the tagging force of the photosensitive adhesive bond layer after B-stage was too strong, and dicing could not be performed.

(Shear strength measurement)

A silicon chip with an adhesive layer (5 × 5 mm each) obtained in the same manner as described above was thermocompression-bonded (200 gf, 120 ° C., 3 seconds) on a separately prepared silicon chip (8 × 8 mm each), and then cured by heating in an oven at 180 ° C. for 1 hour. Was performed. The shear strength in 250 degreeC was measured for the obtained sample using the automatic adhesion tester (the "DAGE SERIES4000" (brand name) by Aktec Co., Ltd.). 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 novolak type epoxy resin

YDF-8170C: Toto Kasei Co., Ltd., bisphenol F type epoxy resin

EP1032H60: JER Corporation, Tris (hydroxyphenyl) methane type solid epoxy resin

Alonix M-140: Toagosei Co., Ltd., N-acryloyloxyethyl hexahydrophthalimide

Fa-220m: hitachi kasei high school, polyethylene glycol # 200 dimethacrylate

I-819: Ciba Japan Co., Ltd., Phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide

I-379EG: Shiba Japan Co., Ltd., 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one

1b2pz: Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole

1: printing plate outer frame
2: resin-embedded portion in the mesh printing plate
3: opening in mesh printing plate
4: Skiing
5: photosensitive adhesive
6: Semiconductor wafer
7: photosensitive adhesive layer
8: Photosensitive adhesive layer staged B 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 bond layer which bonds the 1st-stage semiconductor chip and a support member
17: The photosensitive adhesive bond layer which joins the 2nd semiconductor chip and the 1st semiconductor chip.
18: bonding wire
20: semiconductor wafer with adhesive layer

Claims (9)

Forming a photosensitive adhesive layer by applying a photosensitive adhesive agent to the entirety of one surface of the semiconductor wafer by screen printing;
B-staging the said photosensitive adhesive bond layer by exposure
The manufacturing method of the semiconductor wafer with an adhesive bond layer containing these. The manufacturing method of Claim 1 in which the said photosensitive adhesive agent contains a thermosetting resin, a radiation polymeric compound, and a photoinitiator. The manufacturing method of Claim 1 or 2 in which the said photosensitive adhesive agent further contains a thermosetting initiator. The manufacturing method of any one of Claims 1-3 whose viscosity in 25 degreeC of the said photosensitive adhesive agent is 1-100 Pa.s, and the thixotropy index of the said photosensitive adhesive agent is 1.0-3.0. The photosensitive adhesive agent for using for the manufacturing method of Claim 1 containing a thermosetting resin, a radiation polymeric compound, and a photoinitiator. The photosensitive adhesive agent of Claim 5 which further contains a thermosetting initiator. The photosensitive adhesive agent of Claim 5 or 6 whose viscosity in 25 degreeC is 1-100 Pa.s, and a thixotropy index is 1.0-3.0. The process of individualizing the semiconductor wafer with an adhesive bond layer obtained by the manufacturing method in any one of Claims 1-4, and obtaining a semiconductor chip with an adhesive bond layer,
Bonding a semiconductor chip of the semiconductor chip with an adhesive layer to a support member or another semiconductor chip
A semiconductor device obtained by the method comprising a. The photosensitive adhesive agent for screen printing containing a thermosetting resin, a radiation polymeric compound, and a photoinitiator, the viscosity in 25 degreeC is 1-100 Pa.s, and a thixotropy index is 1.0-3.0.

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