JP2012238700A - Semiconductor wafer with adhesive layer manufacturing method, semiconductor device manufacturing method and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wafer with an adhesive layer manufacturing method which can sufficiently suppress warp of a wafer and efficiently obtain a semiconductor element with an adhesive by dicing, and provide a semiconductor device manufacturing method and a semiconductor device, which can achieve further thinning of the semiconductor device while sufficiently maintaining reliability.SOLUTION: A semiconductor device manufacturing method of the present invention comprises the steps of: providing a photosensitive adhesive layer by coating a liquid photosensitive adhesive containing (A) a radiation polymerizable compound, (B) a photoinitiator and (C) a thermosetting resin on one surface of a semiconductor wafer; and obtaining a semiconductor wafer with an adhesive layer by exposing the photosensitive adhesive layer in an atmosphere at an oxygen concentration of 10% and under to bring the photosensitive adhesive layer to a B-stage.

Description

  The present invention relates to a method for manufacturing a semiconductor wafer with an adhesive layer, a method for manufacturing a semiconductor device, and a semiconductor device.

  In recent years, in addition to downsizing, thinning, and high performance of semiconductor elements, multi-functionalization has progressed, and semiconductor devices in which a plurality of semiconductor elements are stacked are rapidly increasing. A film-like die bonding material (hereinafter referred to as a die bonding film) is applied as a material for bonding between these semiconductor elements or between the lowermost semiconductor element and a substrate (support member).

  In the assembly process of a semiconductor device using a die bonding film, the bonding process on the back surface of the wafer is simplified by using an adhesive sheet in which a dicing sheet is bonded to one surface of the die bonding film.

  Recently, further thinning of semiconductor devices has progressed, and it has been required to further reduce the thickness of adhesive members. However, it is difficult to produce a film-like die bonding material having a thickness of less than 20 μm, and even if it is obtained, handling properties such as winding tend to be reduced.

  On the other hand, a method of forming a B-staged adhesive layer by applying a liquid die bonding material in which an adhesive component is dissolved in a solvent to the back surface of a semiconductor wafer and volatilizing the solvent by heating has been proposed ( For example, see Patent Documents 1 and 2 below).

JP 2007-1110099 A JP 2010-37456 A

  However, in the above method, the wafer is likely to be warped by the heating for forming the B stage. When drying at a low temperature, problems due to heating can be suppressed to some extent. However, in this case, since the residual solvent increases, voids and peeling occur at the time of heat curing, and the reliability tends to decrease. Further, if the B-stage is insufficient, there is a possibility of causing a pickup failure when a semiconductor element with an adhesive is produced by dicing.

  The present invention has been made in view of the circumstances as described above, and a method for producing a wafer with an adhesive layer in which warpage of the wafer is sufficiently suppressed and a semiconductor element with an adhesive can be efficiently obtained by dicing, An object of the present invention is to provide a semiconductor device manufacturing method and a semiconductor device capable of further reducing the thickness of the semiconductor device while maintaining sufficient reliability.

  The present invention applies photosensitive adhesive by applying a liquid photosensitive adhesive containing (A) a radiation polymerizable compound, (B) a photopolymerization initiator, and (C) a thermosetting resin on one surface of a semiconductor wafer. A step of providing an adhesive layer, and a step of obtaining a semiconductor wafer with an adhesive layer by exposing the photosensitive adhesive layer in an atmosphere having an oxygen concentration of 10% or less to form a B-stage. A method for manufacturing a wafer is provided.

  In the present specification, the oxygen concentration means the volume% of the exposed adhesive layer in the environment.

  According to the method for producing a semiconductor wafer with an adhesive layer of the present invention, by using the above-mentioned specific liquid photosensitive adhesive, it is possible to form an adhesive layer that is B-staged by exposure, and for solvent drying. Therefore, even when the wafer is thin, warping can be sufficiently suppressed. Further, in the method of the present invention, it is possible to prevent the photopolymerization initiator from being subjected to oxygen inhibition on the surface of the photosensitive adhesive layer, thereby preventing the surface tack force from being reduced sufficiently. It is possible to form on the semiconductor wafer an adhesive layer having a sufficiently excellent pickup property.

  From the viewpoint of more efficiently reducing the surface tack force of the adhesive layer, it is preferable to expose the photosensitive adhesive layer in an atmosphere having an oxygen concentration of 5% or less. In this case, the manufacturing time of the semiconductor wafer with an adhesive layer can be further shortened.

  The present invention also provides photosensitivity by applying a liquid photosensitive adhesive containing (A) a radiation polymerizable compound, (B) a photopolymerization initiator, and (C) a thermosetting resin on one surface of a semiconductor wafer. A step of providing an adhesive layer; a step of obtaining a semiconductor wafer with an adhesive layer by exposing the photosensitive adhesive layer in an atmosphere having an oxygen concentration of 10% or less to form a B stage; and a semiconductor wafer with an adhesive layer A semiconductor element with an adhesive layer, and a semiconductor element with an adhesive layer and another semiconductor element or a semiconductor element mounting support member sandwiching the adhesive layer of the semiconductor element with an adhesive layer And a step of bonding by pressure bonding.

  In the method for manufacturing a semiconductor device of the present invention, by using the above-mentioned specific liquid photosensitive adhesive, even when the semiconductor wafer is thin, adhesion with sufficiently reduced surface tack force while sufficiently suppressing warpage of the wafer. A semiconductor wafer with an adhesive layer provided with an agent layer is obtained. In addition, the adhesive layer can be easily thinned. By using such a semiconductor wafer with an adhesive layer, it is possible to further reduce the thickness of the semiconductor device while maintaining sufficient reliability.

  The present invention also provides a semiconductor device obtained by the method for manufacturing a semiconductor device of the present invention.

  According to the present invention, a method of manufacturing a wafer with an adhesive layer in which warpage of the wafer is sufficiently suppressed and a semiconductor element with an adhesive can be efficiently obtained by dicing, and further the semiconductor device while maintaining sufficient reliability A manufacturing method of a semiconductor device and a semiconductor device that can be reduced in thickness can be provided.

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. 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. 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.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. In the drawings, the same or corresponding elements are denoted by the same reference numerals, and repeated description is omitted as appropriate. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified, and the dimensional ratio in the drawing is not limited to the illustrated ratio.

1 to 12 are schematic views showing an embodiment of a method for manufacturing a semiconductor device. The manufacturing method according to the present embodiment includes the following steps.
Step 1: A peelable adhesive tape (back grind tape) 4 is laminated on the circuit surface S1 of the semiconductor chip (semiconductor element) 2 formed in the semiconductor wafer 1 (see FIG. 1).
Step 2: The semiconductor wafer 1 is polished from the surface (back surface) S2 opposite to the circuit surface S1 to thin the semiconductor wafer 1 (see FIG. 2).
Step 3: The liquid photosensitive adhesive 5 is applied to the surface S2 opposite to the circuit surface S1 of the semiconductor wafer 1 (see FIG. 3).
Process 4: It exposes from the photosensitive adhesive layer 5 side which consists of the apply | coated liquid adhesive, and makes the photosensitive adhesive layer 5 B-stage (refer FIG. 4). In this way, a semiconductor wafer with an adhesive layer having the adhesive layer 5a is obtained.
Step 5: A peelable adhesive tape (dicing tape) 6 is laminated on the adhesive layer 5a (see FIG. 5).
Step 6: The peelable adhesive tape 4 is peeled off (see FIG. 6).
Step 7: The semiconductor wafer 1 is cut into a plurality of semiconductor chips (semiconductor elements) 2 by dicing (see FIG. 7).
Step 8: The semiconductor chip 2 is picked up and pressure-bonded (mounted) to the semiconductor device support member (semiconductor element mounting support member) 7 or the semiconductor chip (see FIGS. 8, 9, and 10).
Step 9: The mounted semiconductor chip is connected to the external connection terminal on the support member 7 through the wire 16 (see FIG. 11).
Step 10: A stacked body including a plurality of semiconductor chips 2 is sealed with a sealing material 17 to obtain a semiconductor device 100 (see FIG. 12).

  Hereinafter, (Step 1) to (Step 10) will be described in detail.

(Process 1)
A peelable adhesive tape 4 is laminated on the circuit surface S1 side of the semiconductor wafer 1 on which a circuit is formed. Lamination of the adhesive tape 4 can be performed by a method of laminating a film previously formed into a film shape.

(Process 2)
The surface S2 opposite to the adhesive tape 4 of the semiconductor wafer 1 is polished to thin the semiconductor wafer 1 to a predetermined thickness. Polishing is performed using a grinding apparatus 8 in a state where the semiconductor wafer 1 is fixed to a polishing jig by an adhesive tape 4.

(Process 3)
After polishing, the liquid photosensitive adhesive 5 is applied to the surface S2 of the semiconductor wafer 1 opposite to the circuit surface S1. The application can be performed in a state where the semiconductor wafer 1 to which the adhesive tape 4 is attached is fixed to the jig 21 in the box 20. The coating method is selected from a printing method, a spin coating method, a spray coating method, a jet dispensing method, an ink jet method, and the like. Among these, the spin coat method and the spray coat method are preferable from the viewpoints of thinning and film thickness uniformity. A hole may be formed in the suction table included in the spin coater, or the suction table may be mesh-shaped. It is preferable that the suction table has a mesh shape from the point that adsorption marks are difficult to remain. Application by spin coating is preferably performed at a rotational speed of 500 to 5000 rpm in order to prevent the wafer from undulating and the swell of the edge portion. From the same viewpoint, the rotational speed is more preferably 1000 to 4000 rpm. For the purpose of adjusting the viscosity of the liquid photosensitive adhesive, a temperature controller may be provided on the spin coat table.

  The liquid photosensitive adhesive can be stored in a syringe or the like, and a temperature controller may be provided in the syringe set portion of the spin coater.

  When a liquid photosensitive adhesive is applied to a semiconductor wafer by, for example, a spin coating method, an unnecessary liquid photosensitive adhesive may adhere to the edge portion of the semiconductor wafer. Such unnecessary adhesive can be removed by washing with a solvent after spin coating. A cleaning method is not particularly limited, but a method of discharging a solvent from a nozzle to a portion where an unnecessary adhesive is attached while spinning a semiconductor wafer is preferable. Any solvent may be used for the cleaning as long as it dissolves the adhesive. For example, a low boiling point solvent selected from methyl ethyl ketone, acetone, isopropyl alcohol and methanol is used.

  The viscosity at 25 ° C. of the applied liquid photosensitive adhesive is preferably 10 to 30000 mPa · s, more preferably 30 to 10000 mPa · s, still more preferably 50 to 5000 mPa · s, from the viewpoint of thinning the adhesive layer. More preferably, it is 100 to 3000 mPa · s, and most preferably 200 to 1000 mPa · s. When the viscosity is 10 mPa · s or less, the storage stability of the liquid photosensitive adhesive tends to decrease, or pinholes tend to be easily formed in the applied liquid photosensitive adhesive. In addition, it tends to be difficult to make a B-stage by exposure. When the viscosity is 30000 mPa · s or more, it tends to be difficult to make a thin film at the time of coating or to be difficult to discharge. The viscosity here is a value measured using an E-type viscometer at 25 ° C.

(Process 4)
An actinic ray (typically ultraviolet rays) is irradiated from the side of the photosensitive adhesive layer 5 formed from the liquid photosensitive adhesive by coating by the exposure device 9 to make the photosensitive adhesive layer into a B-stage. Thereby, the photosensitive adhesive layer 5 is fixed on the semiconductor wafer 1, and the tack on the surface of the photosensitive adhesive layer 5 can be reduced. The exposure needs to be performed in an atmosphere having an oxygen concentration of 10% or less, and is preferably performed in a vacuum or an atmosphere under an inert gas (for example, nitrogen).

  In the present embodiment, as shown in FIG. 4, the exposure can be performed in a container (for example, an acrylic box) 20 that can be sealed. The container 20 has the vent pipes 22 and 24 in the upper part, and the air in the container can be discharged from the other while blowing nitrogen from one. Thereby, exposure can be performed in an atmosphere having an oxygen concentration of 10% or less. The oxygen concentration can be confirmed by an oxygen concentration meter 26 installed in the container 20. In the present embodiment, it is preferable to keep the oxygen concentration in the container constant while adjusting the flow rate of nitrogen.

  The surface of the adhesive layer is susceptible to oxygen inhibition, and when the oxygen concentration is high, radical species generated by exposure react with oxygen, and the adhesive layer tends not to be sufficiently B-staged. In this embodiment, when the tack force on the surface of the adhesive layer when exposed at a predetermined oxygen concentration is A, and the tack force on the surface of the adhesive layer when exposed at 0% oxygen concentration is B, A / It is preferable to perform exposure at a predetermined oxygen concentration such that B is 1.5 or less. From such a viewpoint, the oxygen concentration during exposure is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less.

The tack force on the surface of the adhesive layer after exposure is measured as follows. First, a liquid photosensitive adhesive is applied onto a silicon wafer by spin coating (2000 rpm / 10 s, 4000 rpm / 20 s), and a release-treated PET film is laminated on the formed photosensitive adhesive layer so that high precision parallelism is achieved. The exposure is performed at 1000 mJ / cm ² using an exposure machine (“EXM-1172-B-∞” (trade name) manufactured by Oak Seisakusho). Thereafter, the tack force on the surface of the adhesive layer at a predetermined temperature (for example, 30 ° C.) was measured using a probe tacking tester manufactured by Reska Co., Ltd., probe diameter: 5.1 mm, peeling speed: 10 mm / s, contact load: 100 gf / Cm ² and contact time: 1 s.

In this embodiment, the tack force (surface tack force) at 30 ° C. on the surface of the adhesive layer after exposure is preferably 200 gf / cm ² or less. Thereby, it becomes sufficiently excellent in the handling property after exposure, the ease of dicing, and the pick-up property. If the tack force at 30 ° C. exceeds 200 gf / cm ² , the adhesiveness of the surface of the adhesive layer at room temperature becomes too high, and the handleability tends to be reduced. There is a tendency that problems such as water permeating into the interface with the adherend and chip jumping occur, and the peelability from the dicing sheet after dicing is lowered and pick-up performance is lowered.

In this embodiment, from the viewpoint of reducing the unreacted photopolymerization initiator in the adhesive layer, the exposure amount is preferably 50 mJ / cm ² or more, and more preferably 100 mJ / cm ² or more.

Moreover, the film thickness of the adhesive layer 5a after exposure is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 10 μm or less, and even more preferably 5 μm or less, from the viewpoint of thinning the adhesive layer. The film thickness of the adhesive layer 5a after exposure can be measured by, for example, the following method. First, a liquid photosensitive adhesive is applied onto a silicon wafer by spin coating (2000 rpm / 10 s, 4000 rpm / 20 s). The obtained coating film is laminated with a release-treated PET film and exposed at 1000 mJ / cm ² with a high-precision parallel exposure machine (Oak Seisakusho, “EXM-1172-B-∞” (trade name)). . Thereafter, the thickness of the adhesive layer is measured using a surface roughness measuring instrument (manufactured by Kosaka Laboratory).

  The 5% weight reduction temperature of the B-staged adhesive layer 5a is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, still more preferably 180 ° C. or higher, and still more preferably 200 ° C. or higher. In order to increase the 5% weight loss temperature, the liquid photosensitive adhesive according to the present invention preferably contains substantially no solvent. If the 5% weight loss temperature is lower than the above lower limit value, the adherend tends to peel off at the time of heat curing after the adherend is bonded or during a heat history such as reflow. Necessary.

The 5% weight loss temperature here is measured as follows. A liquid photosensitive adhesive is applied onto a silicon wafer by spin coating (2000 rpm / 10 s, 4000 rpm / 20 s), and the obtained coating film is laminated with a release-treated PET film to obtain a high-precision parallel exposure machine (Oak Seisakusho). Manufactured by EXM-1172-B-∞ (trade name)) at 1000 mJ / cm ² . Thereafter, the B-staged adhesive layer was measured using a differential thermothermal gravimetric simultaneous measurement device (trade name “TG / DTA6300”, manufactured by SII NanoTechnology Co., Ltd.) and a nitrogen flow ( The 5% weight loss temperature is measured under the condition of 400 ml / min).

In the present embodiment, in order to reduce oxygen inhibition, exposure can be performed in a state where a substrate such as a PET film or a polypropylene film subjected to a release treatment is laminated on the photosensitive adhesive layer 5. In this case, exposure can be performed under conditions where the surface of the photosensitive adhesive layer is shielded from oxygen in the air. Moreover, the process 5 can also be simplified by exposing in the state which laminated | stacked polyvinyl chloride, polyolefin, and an adhesive tape (dicing tape) on the photosensitive adhesive layer. It is also possible to perform exposure through a patterned mask. Exposure can also be performed through a patterned mask. By using a patterned mask, it is possible to form adhesive layers having different fluidity during thermocompression bonding, or to obtain an adhesive pattern by development. The exposure amount is preferably ²⁰ to 2000 mJ / cm ² from the viewpoint of tack reduction and tact time. Moreover, you may heat at the temperature of 100 degrees C or less after exposure for the purpose of the tack | tuck reduction and outgas reduction after B-stage formation.

  The film thickness of the adhesive layer 5a after exposure is preferably 50 μm or less, more preferably 30 μm or less from the viewpoint of reducing stress, and even more preferably 20 μm or less from the viewpoint of film thickness uniformity. The thickness is most preferably 10 μm or less because the package can be made thinner. The film thickness is preferably 0.5 μm or more in order to ensure good thermocompression bonding and adhesion, and 1 μm or more in order to reduce defective bonding such as voids due to dust or cutting residue during dicing. It is more preferable. The film thickness can be measured in the same manner as described above.

  In addition, from the viewpoint of chip handling, stress such as warpage, chip distortion during thermocompression bonding (must be able to be crimped parallel to the substrate), chip retention during curing (distortion due to thermal melting during curing) Therefore, the relationship between the thickness x of the wafer and the thickness y of the adhesive layer preferably satisfies x ≧ y, and more preferably satisfies x ≧ 2 × y.

Also, after exposure, preferably the surface tackiness at 30 ° C. is 200 gf / cm ² or less, more preferably 150 gf / cm ² or less from the viewpoint of tackiness at the time of thermal compression bonding, the dicing tape peeling still more preferred from the viewpoint of sex is 100 gf / cm ² or less, and most preferable from the viewpoint of pickup property is 50 gf / cm ² or less. Further, it is preferable that the surface tack force is 0.1 gf / cm ² or more in order to suppress chip jumping during dicing. The surface tack force can be measured in the same manner as described above.

(Process 5)
After the exposure, a peelable adhesive tape 6 such as a dicing tape is attached to the adhesive layer 5a. The adhesive tape 6 can be attached by a method of laminating an adhesive tape previously formed into a film shape.

(Step 6)
Subsequently, the adhesive tape 4 attached to the circuit surface of the semiconductor wafer 1 is peeled off. For example, an adhesive tape whose adhesiveness is reduced by irradiation with actinic rays (typically ultraviolet rays) is used, and after exposure from the adhesive tape 4 side, it can be peeled off.

(Step 7)
The semiconductor wafer 1 is cut along with the adhesive layer 5a along the dicing line D. By this dicing, the semiconductor wafer 1 is cut into a plurality of semiconductor chips 2 each provided with an adhesive layer 5a on the back surface. Dicing is performed using a dicing blade 11 in a state where the whole is fixed to a frame (wafer ring) 10 with an adhesive tape (dicing tape) 6.

(Process 8)
After dicing, the cut semiconductor chip 2 is picked up together with the adhesive layer 5a by the die bonding apparatus 12, that is, the semiconductor element with the adhesive layer is picked up, and a support member for semiconductor device (support member for mounting semiconductor elements) 7 Alternatively, it is pressure-bonded (mounted) to another semiconductor chip 2. The pressure bonding is preferably performed while heating.

  The semiconductor chip is bonded to the support member or another semiconductor chip by pressure bonding. The shear adhesive strength at 260 ° C. between the semiconductor chip and the supporting member or another semiconductor chip is preferably 0.2 MPa or more, and more preferably 0.5 MPa or more. If the shear bond strength is less than 0.2 MPa, peeling tends to occur due to a thermal history such as a reflow process.

  The shear bond strength here can be measured using a shear bond strength tester “Dage-4000” (trade name). More specifically, for example, it is measured by the following method. First, after exposing the entire surface of the photosensitive adhesive layer made of a liquid photosensitive adhesive applied to a semiconductor wafer, a 3 × 3 mm square semiconductor chip is cut out. The cut-out semiconductor chip with an adhesive layer is placed on a 5 × 5 mm square semiconductor chip prepared in advance, and is pressure-bonded at 120 ° C. for 2 seconds while being pressurized with 100 gf. Thereafter, the sample is heated in an oven at 120 ° C. for 1 hour and then at 180 ° C. for 3 hours to obtain a sample in which the semiconductor chips are bonded to each other. About the obtained sample, the shear adhesive force in 260 degreeC is measured using the shear adhesive strength tester "Dage-4000" (brand name).

(Step 9)
After step 8, each semiconductor chip 2 is connected to an external connection terminal on the support member 7 through a wire 16 connected to the bonding pad.

(Process 10)
The semiconductor device 100 is obtained by sealing the stacked body including the semiconductor chip 2 with the sealing material 17.

  Through the steps as described above, a semiconductor device having a structure in which semiconductor elements and / or a semiconductor element and a semiconductor element mounting support member are bonded can be manufactured. The configuration and the manufacturing method of the semiconductor device are not limited to the above embodiment, and can be appropriately changed without departing from the gist of the present invention.

  For example, the order of steps 1 to 7 can be changed as necessary. More specifically, a liquid photosensitive adhesive is applied to the back surface of a semiconductor wafer diced in advance, and then the photosensitive adhesive layer is B-staged by irradiating with actinic rays (typically ultraviolet rays). You can also. At this time, a patterned mask can also be used.

  The applied liquid photosensitive adhesive may be heated to 120 ° C. or less, preferably 100 ° C. or less, more preferably 80 ° C. or less before or after exposure. Thereby, the remaining solvent and moisture can be reduced, and tack after exposure can be further reduced.

  It is preferable that the 5% weight reduction temperature of the adhesive layer cured by heating after being B-staged by light irradiation is 260 ° C. or higher. If the 5% weight loss temperature is 260 ° C. or lower, peeling tends to occur easily due to a thermal history such as a reflow process.

  After being B-staged by light irradiation, the outgas from the adhesive layer when further cured by heating at 120 ° C. for 1 hour and then at 180 ° C. for 3 hours is preferably 10% or less, and 7% or less. More preferably, it is 5% or less. If the outgas amount is 10% or more, voids and peeling tend to occur during heat curing.

The outgas here is measured as follows. A liquid photosensitive adhesive is applied onto a silicon wafer by spin coating (2000 rpm / 10 s, 4000 rpm / 20 s), and the obtained coating film is laminated with a release-treated PET film to obtain a high-precision parallel exposure machine (Oak Seisakusho). Manufactured by EXM-1172-B-∞ (trade name)) at 1000 mJ / cm ² . Thereafter, the B-staged adhesive layer was lifted under a nitrogen flow (400 ml / min) using a differential thermothermal gravimetric simultaneous measurement apparatus (product name “TG / DTA6300” manufactured by SII Nano Technology). Measures the amount of outgas when heated by a program in which the temperature is raised to 120 ° C. at a temperature rate of 50 ° C./min, held at 120 ° C. for 1 hour, further heated to 180 ° C., and held at 180 ° C. for 3 hours. Is done.

  The minimum melt viscosity at 20 ° C. to 300 ° C. of the adhesive layer B-staged by light irradiation is preferably 30000 Pa · s or less.

Here, the minimum melt viscosity is measured using a viscoelasticity measuring device ARES (manufactured by Rheometrics Scientific F.E. Co., Ltd.) after the exposure with an amount of light of 1000 mJ / cm ² . The minimum value of the melt viscosity at 20 to 300 ° C. The melt viscosity is measured using a parallel plate having a diameter of 8 mm under conditions of a temperature increase of 5 ° C./min, a measurement temperature of 20 ° C. to 300 ° C., and a frequency of 1 Hz.

  The minimum melt viscosity is more preferably 20000 Pa · s or less, further preferably 18000 Pa · s or less, and particularly 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 irregularities. The minimum melt viscosity is preferably 10 Pa · s or more from the viewpoint of handleability.

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

  The liquid photosensitive adhesive of this embodiment is preferably liquid at 25 ° C. and the solvent content is 5% by mass or less. In the present invention, liquid means having fluidity at 25 ° C. and 1 atm.

  The solvent refers to an organic compound that does not have a photoreactive group and a heat-reactive group, has a molecular weight of 500 or less, and is liquid at 25 ° C.

  In the present invention, radiation refers to ionizing radiation or non-ionizing radiation, such as excimer laser light such as ArF and KrF, electron beam extreme ultraviolet light, vacuum ultraviolet light, X-rays, ion beams, i-rays, and g-rays. UV light. As the radiation, ultraviolet light such as i-line or g-line is preferably used from the viewpoint of mass productivity.

  The liquid photosensitive adhesive of this embodiment is preferably liquid at 25 ° C. and the solvent content is 5% by mass or less. The above “solventless type” means that the amount of solvent contained in the adhesive is 5% by mass or less.

  The above solvent is a photopolymerizable group such as radiation polymerizable group, oxime ester group, α-aminoacetophenone, phosphine oxide, epoxy group, phenolic hydroxyl group, carboxyl group, amino group, acid anhydride, isocyanate, peroxide. An organic compound which does not have a thermally reactive group such as diazo group, imidazole or alkoxysilane, has a molecular weight of 500 or less and is liquid at room temperature (25 ° C.). Examples of such solvents include dimethylformamide, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, dioxane, cyclohexanone, ethyl acetate, γ-butyrolactone, and N-methyl-pyrrolidinone.

  When the amount of the solvent falls within the above range, tack can be reduced by light irradiation, and handling properties after light irradiation are improved. Furthermore, foaming during thermocompression bonding or heat curing can be suppressed.

  In the present embodiment, the component (A) is a compound (A1) that is liquid at 25 ° C. and has one carbon-carbon double bond in the molecule (hereinafter sometimes referred to as “A1 compound”). It is preferable to include. In the case of a photosensitive composition containing a compound having two or more carbon-carbon double bonds in the molecule, it is in a state where a crosslinked structure is formed when irradiated with light, and is difficult to melt upon subsequent heating. Since it is difficult to develop, thermocompression bonding tends to be difficult. On the other hand, when a compound having one carbon-carbon double bond in the molecule is contained, sufficient heat fluidity can be obtained and thermocompression bonding can be improved.

  In addition to the compound that is liquid at 25 ° C. and has one carbon-carbon double bond in the molecule, the liquid photosensitive adhesive of this embodiment may further contain a solid acrylate. In this case, the mixture of the component (A) is preferably liquid at 25 ° C.

  Further, from the viewpoint of obtaining a high level of thermal fluidity, it is preferable that a compound having one carbon-carbon double bond in the molecule is contained alone in the adhesive as the radiation polymerizable compound. In addition, when the compound which has one carbon-carbon double bond in a molecule | numerator is used independently, the molecular weight of the polymer obtained after light irradiation can be tens of thousands or more. Here, when a compound having two or more carbon-carbon double bonds is included in the molecule, a network of polymers having a molecular weight of tens of thousands or more is formed, and the adhesiveness and fluidity during heat tend to be reduced. .

  On the other hand, for the purpose of improving heat resistance and reducing tack strength after exposure, a compound having two or more carbon-carbon double bonds in the molecule is compared with a compound having one carbon-carbon double bond in the molecule. Can be used in a proportion of 0.1 to 50% by mass. In this case, as a compound having two or more carbon-carbon double bonds in the molecule to be used in combination, from the viewpoint of thermal fluidity, an aliphatic acrylate having 10 or more carbon atoms, from the viewpoint of adhesiveness when heated An acrylate having an aromatic or cyclic structure such as an isocyanuric ring or cyclohexyl having a functional group equivalent of 200 g / eq or more and more preferably 300 g / eq or more is preferable from the viewpoint of low stress.

  The component (A) preferably has a viscosity at 25 ° C. of 5000 mPa · s or less from the viewpoint of the solubility of the other components such as the component (B) and the component (C), and further reduces the thickness. From the viewpoint of improving adhesion by adding a large amount of a solid or high-viscosity thermosetting resin, it is more preferably 1000 mPa · s or less, and even more preferably 2000 mPa · s or less. Most preferably: The viscosity here is the value of the entire component (A) contained in the liquid photosensitive adhesive, using an EHD type rotational viscometer manufactured by Tokyo Keiki Seisakusho, and a sample amount of 0.4 mL and a condition of 3 ° cone. Below, it is the value of the viscosity measured at 25 degreeC.

  When the viscosity of the component (A) exceeds 5000 mPa · s, the viscosity of the liquid photosensitive adhesive tends to increase, making it difficult to reduce the thickness of the liquid photosensitive adhesive or to eject the liquid from a nozzle of a coating apparatus or the like. . From the viewpoint of preventing the generation of pinholes during application and ensuring heat resistance, the viscosity of the component (A) at 25 ° C. is preferably 10 mPa · s or more.

  The component (A) preferably has a 5% weight loss temperature of 100 ° C. or higher, more preferably 120 ° C. or higher, and is generated by volatilization of the unreacted component (A) during thermosetting. It is still more preferable that it is 150 degreeC or more at the point which can suppress peeling and a void, and it is most preferable that it is 180 degreeC or more. The 5% mass reduction temperature here is a value of the entire component (A) contained in the liquid photosensitive adhesive, and the component (A) is subjected to differential thermothermal gravimetric simultaneous measurement apparatus (manufactured by SII NanoTechnology: TG). / DTA6300) is a 5% weight loss temperature when measured at a temperature elevation rate of 10 ° C./min and under a nitrogen flow (400 ml / min).

  In addition, from the viewpoint of lowering the viscosity of the liquid photosensitive adhesive, suppressing surface unevenness after coating, and fluidity during heating after B-stage, a material design mainly comprising an organic compound is preferable. The 5% weight loss temperature is preferably 500 ° C. or lower.

In addition, the component (A) is a polymer obtained by polymerizing the component (A) having a Tg of 100 ° C. or less from the viewpoint of low-temperature thermocompression after B-stage and fluidity during heat. It is preferable that the Tg is 20 ° C. or higher from the viewpoint of the handleability after B-stage formation and the pick-up property. Tg of the polymer of component (A) was obtained by dissolving I-379EG (manufactured by Ciba Japan), which is a photoinitiator, in component (A) at a ratio of 3% by mass based on the total amount of the liquid photosensitive adhesive. The composition was applied on a PET (polyethylene terephthalate) film so as to have a film thickness of 30 μm, and this coating film was subjected to a high-precision parallel exposure machine (trade name: EXM-1172-B-, manufactured by Oak Seisakusho) at 25 ° C. under air. ∞), a laminate obtained by laminating a film obtained by exposure at 1000 mJ / cm ² to a film thickness of 150 μm, a viscoelasticity measuring device (Rheometrics Scientific F.E. Co., Ltd., product) Name: tan δ peak temperature at −50 ° C. to 200 ° C. measured using ARES). The measurement plate is a parallel plate having a diameter of 8 mm, and the measurement conditions are a heating rate of 5 ° C./min, a measurement temperature of −50 ° C. to 200 ° C., and a frequency of 1 Hz.

  The liquid photosensitive adhesive of this embodiment has a weight average molecular weight of 50,000 to 1,000,000 when irradiated with light from the viewpoints of adhesion to an adherend, reduction of surface tack, dicing, and improvement of high-temperature adhesion after curing. It is preferable that the polymer of the said (A) component which is is contained. Further, from the viewpoint of thermocompression bonding with the adherend, it is preferable that a polymer of the component (A) having a weight average molecular weight of 5,000 to 500,000 when irradiated with light. In addition, the said weight average molecular weight means the weight average molecular weight when measured in polystyrene conversion using the Shimadzu Corporation high performance liquid chromatography "C-R4A" (brand name).

  The weight average molecular weight of the polymer of component (A) is the exposure conditions (oxygen concentration, temperature, strength), the amount of photoinitiator, the addition of thiol, phenolic hydroxyl group, amine or phenolic polymerization inhibitor, the type of acrylate and the heat. It can adjust with the compounding quantity of curable resin, and the viscosity of an adhesive composition.

  Examples of the component (A) used in this embodiment include compounds having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadiimide group, (meth) acryl group and the like. From the viewpoint of reactivity, the component (A) preferably contains a monofunctional (meth) acrylate as the A1 compound. The monofunctional here means having one carbon-carbon double bond in the molecule, and may have other functional groups.

  The monofunctional (meth) acrylate preferably has a 5% weight loss temperature of 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. In addition, from the viewpoints of lowering the viscosity of the liquid photosensitive adhesive, suppressing surface irregularities after coating, and fluidity during hot processing after B-stage, the material design mainly composed of organic compounds is preferable, so monofunctional (meth) acrylate The 5% weight loss temperature is preferably 500 ° C. or less. The 5% mass reduction temperature of the monofunctional (meth) acrylate was measured using a differential thermothermal gravimetric simultaneous measurement apparatus (manufactured by SII NanoTechnology: TG / DTA6300) with a temperature rising rate of 10 ° C./min and a nitrogen flow (400 ml / min) is the 5% weight loss temperature as measured under.

  By blending a monofunctional (meth) acrylate having a 5% weight loss temperature in the above temperature range, the unreacted monofunctional (meth) acrylate remaining after being B-staged by exposure is volatilized during thermocompression bonding or thermosetting. This can be suppressed.

  Examples of the monofunctional (meth) acrylate as the A1 compound include, for example, glycidyl group-containing (meth) acrylate, 4-hydroxyphenyl methacrylate, 3,5-dimethyl-4-hydroxybenzylacrylamide, and the like in that the cured product can be toughened. Carboxyl group-containing (meth) acrylates such as phenolic hydroxyl group-containing (meth) acrylate, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxypropylhexahydrophthalic acid, and 2-methacryloyloxymethylhexahydrophthalic acid Phenol EO-modified (meth) acrylate, phenol PO-modified (meth) acrylate, nonylphenol EO-modified (meth) acrylate, nonylphenol PO-modified (meth) acrylate, phenoxy in that heat resistance can be improved Ethyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, hydroxyethylated phenylphenol acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol ( Aromatic-containing (meth) acrylates such as (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, benzyl (meth) acrylate, 2-methacryloyloxyethyl 2-hydroxypropyl phthalate, and phenylphenol glycidyl ether acrylate are preferred, and B stage 2-hydride in that it can provide adhesion after conversion and adhesion after thermosetting Xyl-3-phenoxypropyl (meth) acrylate, o-phenylphenol glycidyl ether (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl- Hydroxyl group-containing (meth) acrylate represented by the following general formula (A-1) or (A-2) such as phthalic acid, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (1,2-cyclohexa) An imide group-containing (meth) acrylate represented by the following general formula (A-3) or (A-4), such as carboximido) ethyl acrylate, is preferred, and an isoboronyl-containing (meta) group can be used to reduce the viscosity of the liquid photosensitive adhesive. ) Acrylate, dicyclopentadienyl group-containing (meth) acrylate, Soboronyl (meth) acrylate is preferable.

In the general formulas (A-1) and (A-2), R ₁ represents a hydrogen atom or a methyl group, R ₃ represents a monovalent organic group, and R ₂ and R ₄ each represents a divalent organic group. Indicates. R ₃ preferably has an aromatic group from the viewpoint of heat resistance. R ₄ preferably has an aromatic group from the viewpoint of heat resistance.

In the general formulas (A-3) and (A-4), R ₁ represents a hydrogen atom or a methyl group, R ₅ represents a divalent organic group, and R ₆ , R ₇ , R ₈ , R ₉ are Each represents a monovalent hydrocarbon group having 1 to 30 carbon atoms, R ₆ and R ₇ may be bonded to each other to form a ring, and R ₈ and R ₉ may be bonded to each other to form a ring; May be. When R ₆ and R ₇ , and R ₈ and R ₉ form a ring, examples thereof include a benzene ring structure and an alicyclic structure. The benzene ring structure and the alicyclic structure may have a thermosetting group such as a carboxyl group, a phenolic hydroxyl group, and an epoxy group, or may have an organic group such as an alkyl group.

  The compounds represented by the general formulas (A-3) and (A-4) are, for example, an N-hydroxyalkylimide compound obtained by reacting a monofunctional acid anhydride and ethanolamine, an acrylate ester or an acrylic ester. It can be synthesized by reacting with an acid ester by a known method. In this case, as the monofunctional acid anhydride, 4-phenylethynylphthalic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 2,5-norbornadiene- 2,3-dicarboxylic acid anhydride, maleic acid anhydride, trimellitic acid anhydride, cyclohexanedicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, cis-norbornene-endo-2,3-dicarboxylic acid Dicarboxylic anhydrides such as acid hexahydrophthalic anhydride, hexahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, etc. Can be used. Examples of the N-hydroxyalkylimide compound include N-hydroxyethylphthalimide and N-hydroxyethyl succinimide.

  The compounds represented by the above general formulas (A-3) and (A-4) include storage stability, low tack after B-stage, adhesion after B-stage, heat resistance after thermosetting, adhesion From the viewpoints of properties and reliability, compounds represented by the following general formulas (A-5) to (A-9) can be used as preferable ones, and from the viewpoint of low viscosity, the following general formula (A-5), The compounds represented by (A-7) to (A-9) can be used as more preferable ones.

上記式（Ａ−５）〜（Ａ−９）中、Ｒ１は、水素原子又はメチル基を示す。

In the above formulas (A-5) to (A-9), R1 represents a hydrogen atom or a methyl group.

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

  Monofunctional (meth) acrylates with epoxy groups have a 5% weight loss temperature during film formation from the viewpoints of storage stability, adhesion, assembly heating and low outgassing of the package after assembly, heat resistance and moisture resistance. It is preferably 150 ° C. or higher in that it can suppress volatilization or segregation on the surface due to heat drying, and it is further 180 ° C. or higher in that it can suppress voids and peeling due to outgassing during thermosetting and decrease in adhesion. Preferably, it is more preferably 200 ° C. or higher in terms of suppressing voids and peeling in the thermal history, and 260 ° C. or higher in terms of suppressing voids and peeling due to volatilization of unreacted components during reflow. Most preferred. As such a monofunctional (meth) acrylate having an epoxy group, a compound having an aromatic ring in the molecule is preferable. Moreover, the said heat resistance can be satisfied by using a polyfunctional epoxy resin whose 5% weight reduction temperature is 150 degreeC or more as a raw material.

  Examples of the monofunctional (meth) acrylate having an epoxy group include glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl methacrylate glycidyl ether, functional groups that react with epoxy groups, and ethylenic groups. Examples thereof include compounds obtained by reacting a compound having a saturated 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. More specifically, for example, in the presence of triphenylphosphine or tetrabutylammonium bromide, a polyfunctional epoxy resin having at least two or more epoxy groups in one molecule and 0.1 to 0 with respect to 1 equivalent of epoxy groups. Obtained by reacting with 9 equivalents 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.

  In addition, 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, particularly 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 Ester, 3 glycidylamine functional type (or tetrafunctional) include those glycidyl amines of naphthalene resins as a raw material.

In particular, the number of epoxy groups is preferably 3 or less in order to improve thermocompression bonding, low stress properties, and adhesion. Although it does not specifically limit as such a compound, The compound etc. which are represented by the following general formula (A-10), (A-11), (A-12), (A-13) or (A-14) Is preferably used. In the following general formulas (A-10) to (A-14), R ¹² and R ¹⁶ represent a hydrogen atom or a methyl group, and R ¹⁰ , R ¹¹ , R ¹³ and R ¹⁴ represent a divalent organic group. R ¹⁵ is an organic group having an epoxy group, and R ¹⁷ and R ¹⁸ are each an organic group having an ethylenically unsaturated group, and the rest are organic groups having an epoxy group. Further, f in (A-13) represents an integer of 0 to 3.

  It is preferable that content of said monofunctional (meth) acrylate is 20-100 mass% with respect to (A) component whole quantity, It is more preferable that it is 40-100 mass%, It is 50-100 mass%. Most preferably it is. By setting the blending amount of the monofunctional (meth) acrylate within the above range, it is possible to improve adhesion and thermocompression bonding with the adherend after the B-stage.

  In the liquid photosensitive adhesive of this embodiment, the compound which is liquid at 25 ° C. and has one carbon-carbon double bond in the molecule may be blended alone or in combination of two or more. it can.

  The A1 compound preferably has a viscosity at 25 ° C. of 5000 mPa · s or less from the viewpoint of solubility of other components such as the component (B) and the component (C). More preferably, it is 3000 mPa · s or less, and even more preferably 2000 mPa · s or less. Further, from the viewpoint of improving adhesion by adding a large amount of a solid or high viscosity thermosetting resin, it is 1000 mPa · s or less. Most preferably it is. The viscosity here is the value for the A1 compound, and the viscosity value measured at 25 ° C. under the conditions of a sample volume of 0.4 mL and a 3 ° cone using an EHD type rotational viscometer manufactured by Tokyo Keiki Seisakusho. It is.

  When the viscosity of the A1 compound exceeds 5000 mPa · s, the viscosity of the adhesive composition tends to increase, making it difficult to reduce the film thickness, or making it difficult to discharge from a nozzle of a coating apparatus or the like. From the viewpoint of preventing the generation of pinholes during application and ensuring heat resistance, the viscosity of the A1 compound at 25 ° C. is preferably 10 mPa · s or more.

  In addition, the viscosity of the A1 compound is preferably 1000 mPa · s or less from the viewpoint of improving dischargeability when the adhesive composition is discharged from a nozzle or the like and reducing the film thickness, and 5 mPa · s from the viewpoint of reducing outgas. The above is preferable.

  The A1 compound preferably has a 5% weight loss temperature of 100 ° C. or higher, more preferably 120 ° C. or higher, even more preferably 150 ° C. or higher, and 180 ° C. or higher. Most preferred. Here, the 5% mass reduction temperature means that the A1 compound was heated at a rate of temperature increase of 10 ° C./min, a nitrogen flow (400 ml / 400 ml) using a differential thermothermal gravimetric simultaneous measurement apparatus (manufactured by SII Nanotechnology: TG / DTA6300). min) is the 5% weight loss temperature as measured under.

  In addition, from the viewpoint of lowering the viscosity of the liquid photosensitive adhesive, suppressing surface irregularities after coating, and fluidity during heating after B-stage, a material design mainly composed of an organic compound is preferable. The weight loss temperature is preferably 500 ° C. or less.

Furthermore, the A1 compound is preferably one in which the Tg of the polymer obtained by polymerizing the A1 compound is 100 ° C. or lower from the viewpoint of low-temperature thermocompression bonding and hot fluidity after B-stage formation. From the viewpoint of later pickup properties, those having a Tg of 20 ° C. or higher are preferred. The Tg of the polymer of the A1 compound is a PET (polyethylene terephthalate) obtained by dissolving a photoinitiator I-379EG (manufactured by Ciba Japan) in a proportion of 3% by mass with respect to the A1 component. ) It was applied on the film so as to have a film thickness of 30 μm, and this coating film was exposed at 1000 mJ / cm ² using a high precision parallel exposure machine (Oak Seisakusho, trade name: EXM-1172-B-∞). The laminate obtained by laminating the obtained film to a film thickness of 150 μm was measured using a viscoelasticity measuring device (manufactured by Rheometrics Scientific F.E., trade name: ARES). It is a tan δ peak temperature at −50 ° C. to 200 ° C. The measurement plate is a parallel plate having a diameter of 8 mm, and the measurement conditions are a heating rate of 5 ° C./min, a measurement temperature of −50 ° C. to 200 ° C., and a frequency of 1 Hz.

  The liquid photosensitive adhesive of this embodiment may contain (meth) acrylate more than bifunctional as (A) radiation-polymerizable compound other than said A1 compound. Bifunctional or more here means having two or more carbon-carbon double bonds in the molecule. 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 (A-15), urethane acrylate Or urethane methacrylate, urea acrylate, etc. are mentioned.

上記一般式（Ａ−１５）中、Ｒ^１９及びＲ^２０は各々独立に、水素原子又はメチル基を示し、ｇ及びｈは各々独立に、１〜２０の整数を示す。

In the general formula (A-15), 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.

In addition, a compound in which R ¹⁵ in the above formula (A-12) is an organic group having an ethylenically unsaturated group, and two or more of R ^{17 in} the above formula (A-13) have an ethylenically unsaturated group. A compound in which the remainder is an organic group having an epoxy group, and two or more of R ¹⁸ in the formula (A-14) are organic groups having an ethylenically unsaturated group, and the rest Is an organic group having an epoxy group.

  In addition, the liquid photosensitive adhesive of this embodiment can contain a monofunctional maleimide compound represented by the following structural formula for the purpose of reducing tack after exposure and improving adhesiveness.

  The content of the component (A) is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and most preferably 40 to 90% by mass with respect to the total amount of the adhesive. When the content of the component (A) is less than 10% by mass, the surface tack force after exposure tends to increase, and when it exceeds 95% by mass, the adhesive strength after thermosetting tends to decrease. .

  As said (B) photoinitiator, the compound which produces | generates a radical, an acid, a base, etc. by light irradiation can be used. Among them, from the viewpoint of corrosion resistance such as migration, it is preferable to use a compound that generates radicals and / or bases by light irradiation. In particular, radicals are used in that heat treatment after exposure is unnecessary and sensitivity is high. The resulting compound is preferably used. A compound that generates an acid or a base by light irradiation can exhibit a function of promoting polymerization and / or reaction of an epoxy resin.

  The photopolymerization initiator preferably has a molecular extinction coefficient with respect to light having a wavelength of 365 nm of 100 ml / g · cm or more in terms of enabling B-stage, and 200 ml / g in terms of further reducing tack after exposure. More preferably, it is not less than cm, more preferably not less than 400 ml / g · cm in that oxygen inhibition can be further reduced, and 1000 ml / g in that B-stage can be achieved in a low exposure amount in a short time. Most preferred is g · cm or more. Note that the time required for the B-stage is preferably within 60 s, and more preferably within 30 s in terms of more efficient production of semiconductor materials. For the molecular extinction coefficient, a 0.001 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 the component (B) include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy)- Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2 -Methyl-propan-1-one, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] ethyl ester, phenylglyoxylic acid methyl ester, 2-dimethylamino-2- (4 -Methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-ethylhexyl-4-di Tylaminobenzoate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl -Ketones, aromatic ketones such as 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1,2,4-diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone, benzyldimethyl ketal, etc. Benzyl derivative, 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- (o-methoxyphenyl) Nyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer , 2,4,5-triarylimidazole dimer such as 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9, Acridine derivatives such as 9'-acridinyl) heptane, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6, -trimethylbenzoyl) -phenylphosphine Examples thereof include bisacylphosphine oxides such as oxides and compounds having maleimide. These can be used alone or in combination of two or more.

  Among the photoinitiators described above, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-, in terms of solubility in an adhesive composition containing no solvent. 1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane -1-one is preferably used.

  The component (B) is preferably a compound having an oxime ester skeleton or a morpholine skeleton in the molecule from the viewpoint that B-stage can be efficiently formed by exposure. Although it does not specifically limit as such a compound, The compound which has an oxime ester group represented by the following general formula (B-1), and / or the following general formula (B-2), (B-3) or (B- A compound having a morpholine ring represented by 4) is preferred. Specifically, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4- (Methylthio) phenyl) -2-morpholinopropan-1-one is preferably used.

式中、Ｒ^５１及びＲ^５２はそれぞれ独立に、水素原子、炭素数１〜７のアルキル基、又は芳香族系炭化水素基を含む有機基を示し、Ｒ^５３及びＲ^５４及びＲ^５５は、炭素数１〜７のアルキル基、又は芳香族系炭化水素基を含む有機基を示し、Ｒ^５６及びＲ^５７は、芳香族系炭化水素基を含む有機基を示す。

In the formula, R ⁵¹ and R ⁵² each independently represent a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or an organic group containing an aromatic hydrocarbon group, and R ^53, R ^54, and R ⁵⁵ represent carbon number 1-7 alkyl group, or an organic group containing an aromatic hydrocarbon group, R ⁵⁶ and R ⁵⁷ are an organic group containing an aromatic hydrocarbon group.

  Although it does not restrict | limit especially as said aromatic hydrocarbon group, For example, a phenyl group and a naphthyl group, a benzoin derivative, a carbazole derivative, a thioxanthone derivative, a benzophenone derivative etc. are mentioned. Moreover, the aromatic hydrocarbon group may have a substituent.

  Particularly preferable as the component (B) is a compound having an oxime ester group and / or a morpholine ring, having a molecular extinction coefficient of 1000 ml / g · cm or more with respect to light having a wavelength of 365 nm, and a 5% mass reduction temperature. It is a compound of 150 ° C. or higher.

  Examples of such component (B) include compounds represented by the following structural formulas (B-5) to (B-9).

  When the liquid photosensitive adhesive of this embodiment contains an epoxy resin, the component (B) may contain a photoinitiator that exhibits a function of promoting polymerization and / or reaction of the epoxy resin by irradiation with radiation. Good. 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 the photobase generator, the high-temperature adhesiveness and moisture resistance of the adhesive to the adherend can be further improved. This is because the base generated from the photobase generator acts as a curing catalyst for the epoxy resin efficiently, so that the crosslinking density can be further increased, and the generated curing catalyst corrodes the substrate and the like. This is thought to be because there are few. Moreover, by including a photobase generator in the adhesive, the crosslink density can be improved, and the outgas during standing at high temperature can be further reduced. Furthermore, the curing process temperature can be lowered and shortened.

  The photobase generator may be a compound that generates a base when irradiated with radiation. As the base to be generated, a strongly basic compound is preferable in terms of reactivity and curing speed. More specifically, the pKa value in the aqueous solution of the base generated by the photobase generator is preferably 7 or more, and more preferably 8 or more. pKa is generally the logarithm of the acid dissociation constant as a basic indicator.

  Examples of the base generated upon irradiation 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-dimethylpiperidine. Piperidine derivatives such as proline derivatives, trialkylamine derivatives such as trimethylamine, triethylamine, and triethanolamine, pyridine derivatives substituted with an amino group or alkylamino group at the 4-position, such as 4-methylaminopyridine, 4-dimethylaminopyridine, Pyrrolidine derivatives such as pyrrolidine and n-methylpyrrolidine, dihydropyridine derivatives, triethylenediamine, alicyclic amine derivatives such as 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU), benzines Methylamine, benzyl dimethylamine, and the like benzylamine derivatives such as benzyl diethylamine.

  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 highly basic trialkylamines by irradiation with actinic rays, 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 are 2,4-dimethoxy-1,2-diphenylethane-1-one, 1,2-octanedione, 1- [4- (phenylthio)-, 2- Oxime derivatives such as (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and light 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl, which is commercially available as a radical generator -1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butano -1, hexaarylbisimidazole derivatives (halogen, alkoxy group, nitro group, or a substituted group such as a cyano group substituted by a phenyl group), 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 an adhesive.

  The above photobase generator does not exhibit reactivity with the epoxy resin when not exposed to light, and therefore has excellent storage stability at room temperature.

  The content of the component (B) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A). It is more preferable that it is 5-10 mass parts. If this content exceeds 20 parts by mass, the outgas will increase and the adhesiveness will tend to decrease, and the storage stability will tend to decrease. On the other hand, when the content is less than 0.1 parts by mass, it tends to be difficult to make a B stage.

  In the liquid photosensitive adhesive of this embodiment, a sensitizer can be used in combination 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, Examples thereof include a compound containing an azide group. These can be used alone or in combination of two or more.

  The (C) thermosetting resin is not particularly limited as long as it is a component composed of a reactive compound that undergoes a crosslinking reaction by heat. 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, thermosetting by trimerization of aromatic dicyanamide Tree Etc. The. Among these, epoxy resins, maleimide resins, and allyl nadiimide resins are preferable because they can have excellent adhesive strength at high temperatures. In addition, a thermosetting resin can be used individually 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 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 pentadienephenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) glycidylamine, glycidylamine of naphthalene resin, etc. It is. These can be used alone or in combination of two or more.

  As the epoxy resin, it is possible to use a high-purity product in which impurity ions such as alkali metal ions, alkaline earth metal ions, halogen ions, particularly chlorine ions and hydrolyzable chlorine are reduced to 300 ppm or less. From the viewpoint of prevention and corrosion prevention of metal conductor circuits.

  Examples of the maleimide resin include a bismaleimide resin represented by the following general formula (I) and a novolac maleimide resin represented by the following general formula (II).

［式（Ｉ）中、Ｒ_５は芳香族環及び／又は直鎖、分岐若しくは環状脂肪族炭化水素を含む２価の有機基を示す。］

[In the formula (I), R ₅ represents a divalent organic group containing an aromatic ring and / or a linear, branched or cyclic aliphatic hydrocarbon. ]

R ₅ includes a divalent organic group represented by the following chemical formula. In each formula, n is an integer of 1-10.

［式（ＩＩ）中、ｎは０〜２０の整数を示す。］

[In formula (II), n represents an integer of 0 to 20. ]

  Among them, a bismaleimide resin represented by the following structural formula (III) and / or a novolak maleimide represented by the above general formula (II) is able to impart heat resistance and high-temperature adhesive strength after curing of the adhesive layer. Resins are preferably used.

  For curing the maleimide resin, an allylated bisphenol A, a cyanate ester compound or the like can be used in combination, or a catalyst such as a peroxide can be added. About the addition amount of the said compound and a catalyst, and the presence or absence of addition, it adjusts suitably in the range which can ensure the target characteristic.

  As the allyl nadiimide resin, a compound containing two or more allyl naimide groups in the molecule can be used, and examples thereof include a bisallyl nadiimide resin represented by the following general formula (IV).

［式（ＩＶ）中、Ｒ_１は芳香族環及び／又は直鎖、分岐若しくは環状脂肪族炭化水素を含む２価の有機基を示す。］

[In formula (IV), R ₁ represents a divalent organic group containing an aromatic ring and / or a linear, branched or cyclic aliphatic hydrocarbon. ]

Examples of R ₁ include a divalent organic group represented by the following chemical formula. In each formula, n is an integer of 1-10.

  Among them, liquid hexamethylene type bisallyl nadiimide represented by the following structural formula (V) and low melting point (melting point: 40 ° C.) solid xylylene type bisallyl nadiimide represented by the following structural formula (VI) , Which is preferable in terms of providing good hot fluidity. Solid xylylene-type bisallylnadiimide can suppress the increase in adhesiveness after B-stage in addition to good fluidity during heat treatment, handling property, and easy release from dicing tape during pick-up. It is more preferable in terms of suppressing re-fusion of the cut surface after dicing.

  Said bisallyl nadiimide can be used individually or in combination of 2 or more types.

  The allyl nadiimide resin described above requires a curing temperature of 250 ° C. or higher when singly cured in the absence of a catalyst, which is a major obstacle to practical use. Only metal corrosive catalysts, which are a serious drawback in electronic materials such as onium salts and onium salts, can be used, and final curing requires a temperature of around 250 ° C. It is possible to cure at a low temperature of 200 ° C. or less by using any one of the acrylate compound, methacrylate compound, or maleimide resin (Reference: A. Renner, A. Kramer, “Allylnadic-Imides: A New Class”). of Heat-Resistant Thermosets ", J. Polym. Sci., Part A Polym.Chem., 27, 1301 (1989)).

  (C) The thermosetting resin can be used regardless of liquid or solid at room temperature. In the case of a liquid thermosetting resin, the viscosity can be further reduced, and in the case of a solid thermosetting resin, tack after light irradiation can be further reduced. Moreover, you may use together a liquid thermosetting resin and a solid thermosetting resin.

  When a liquid thermosetting resin is used, the viscosity is preferably 10,000 mPa · s or less, more preferably 5000 mPa · s or less, still more preferably 3000 mPa · s or less, and even more preferably 2000 mPa · s or less. Most preferably. When the viscosity exceeds 10,000 mPa · s, the viscosity of the adhesive increases, and it tends to be difficult to reduce the thickness. Such a liquid thermosetting resin is not particularly limited, but is preferably an epoxy resin from the viewpoint of adhesiveness and heat resistance, and particularly a trifunctional (or tetrafunctional) glycidylamine or bisphenol A type (or AD type, S type, and F type glycidyl ethers are preferably used.

  When using a solid thermosetting resin, it can be dissolved in the component (A), for example. Although it does not specifically limit as solid thermosetting resin, From a viewpoint of thermocompression bonding property and viscosity, it is preferable that molecular weight is 2000 or less, Preferably it is 1000 or less, and a softening point is 100 degrees C or less, Preferably it is 80 degrees C The following is preferable. In addition, a trifunctional or higher functional epoxy resin is preferable from the viewpoint of adhesiveness and heat resistance. As such an epoxy resin, for example, an epoxy resin having the following structure is preferably used.

ｎは、０〜１０の整数を示す。

n shows the integer of 0-10.

  The (C) thermosetting resin preferably has a 5% weight loss 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 of the thermosetting resin means that the thermosetting resin is heated at a rate of 10 ° C./temperature using a differential thermothermal gravimetric simultaneous measurement apparatus (manufactured by SII Nanotechnology: TG / DTA6300). Min, 5% weight loss temperature when measured under a nitrogen flow (400 ml / min). By applying a thermosetting resin having a high 5% weight loss temperature, volatilization during thermocompression bonding or thermosetting can be suppressed. As the thermosetting resin having such heat resistance, an epoxy resin having an aromatic group in the molecule is exemplified, and in particular from the viewpoint of adhesion and heat resistance, trifunctional (or tetrafunctional) glycidylamine, Bisphenol A type (or AD type, S type, F type) glycidyl ether is preferably used.

  (C) It is preferable that it is 1-100 mass parts with respect to 100 mass parts of (A) component, and, as for content of a thermosetting resin, it is more preferable that it is 2-50 mass parts. When this content exceeds 100 parts by mass, the tack after exposure tends to increase. On the other hand, when the content is less than 2 parts by mass, there is a tendency that sufficient high-temperature adhesiveness cannot be obtained.

  The liquid photosensitive adhesive of this embodiment preferably further contains a curing accelerator. The curing accelerator is not particularly limited as long as it is a compound that accelerates curing / polymerization of the epoxy resin by heating. For example, a phenol compound, an aliphatic amine, an alicyclic amine, an aromatic polyamine, polyamide, an aliphatic 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, 1,8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate, tertiary amine and the like. Among these, imidazoles are preferably used from the viewpoint of solubility and dispersibility when no solvent is contained. As for content of a hardening accelerator, 0.01-50 mass parts is preferable with respect to 100 mass parts of epoxy resins. Also, imidazoles are particularly preferable from the viewpoints of adhesiveness, heat resistance, and storage stability.

  As imidazoles, the reaction initiation temperature is preferably 50 ° C. or higher, and more preferably 80 ° C. or higher. When the reaction start temperature is 50 ° C. or lower, the storage stability is lowered, so that the viscosity of the adhesive rises and it becomes difficult to control the film thickness.

  As imidazoles, it is preferable to use imidazoles that are soluble in epoxy resins. By using such imidazole, a coating film with less unevenness can be obtained. Such imidazoles are not particularly limited, but 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole and the like. From the viewpoints of storage stability, adhesiveness, and heat resistance, 1-benzyl-2-phenylimidazole is particularly preferably used.

  As the imidazoles, a compound pulverized to an average particle size of preferably 10 μm or less, more preferably 8 μm or less, and most preferably 5 μm or less can be used. By using imidazoles having such a particle size, the viscosity change of the adhesive can be suppressed, and precipitation of imidazoles can be suppressed. In addition, when the thin film is formed, surface irregularities can be reduced, and thereby a uniform film can be obtained. Furthermore, since the curing in the resin can proceed uniformly during curing, outgas can be reduced.

  Moreover, the liquid photosensitive adhesive of this embodiment 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 compound, trisphenol compound, tetrakisphenol novolak, bisphenol. A novolak, poly-p-vinylphenol, phenol aralkyl resin and the like. Among these, those having a number average molecular weight in the range of 400 to 4000 are preferable. Thereby, the outgas at the time of heating which causes the contamination of the semiconductor element or the device at the time of assembling the semiconductor device can be suppressed. The phenolic compound is preferably liquid, and the allyl-modified phenol novolak is preferably used because it is liquid and highly heat resistant.

  The content of the phenolic compound is preferably 50 to 100 parts by mass and more preferably 60 to 95 parts by mass with respect to 100 parts by mass of the thermosetting resin.

  The liquid photosensitive adhesive of this embodiment can further contain (D) a thermal radical generator. 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 adhesive composition, film forming temperature, pressure bonding, curing conditions, other process conditions, storage stability, and the like. Although it does not specifically limit as a peroxide which can be used, For example, 2,5-dimethyl-2,5-di (t-butylperoxyhexane), dicumyl peroxide, t-butylperoxy-2 -Ethyl hexanate, t-hexyl peroxy-2-ethyl hexanate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexyl peroxy) ) -3,3,5-trimethylcyclohexane, bis (4-t-butylcyclohexyl) peroxydicarbonate, etc., and one of these may be used alone or in combination of two or more. it can. By containing the above organic peroxide, the unreacted radiation-polymerizable compound remaining after exposure can be reacted, and low outgassing and high adhesion can be achieved.

  Examples of the thermal radical generator having a one-minute half-life temperature of 80 ° C. or higher include perhexa 25B (manufactured by NOF Corporation), 2,5-dimethyl-2,5-di (t-butylperoxyhexane) ( 1 minute half-life temperature: 180 ° C.), Parkmill D (manufactured by NOF Corporation), dicumyl peroxide (1 minute half-life temperature: 175 ° C.), and the like.

  (D) The content of the thermal radical generator is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and more preferably 0.5 to 5%, based on the total amount of the (A) radiation polymerizable compound. Mass% is most preferred. When the content of the thermal radical generator is less than 0.01% by mass, the curability is lowered and the effect of addition is reduced, and when it exceeds 5% by mass, the outgas amount is increased and the storage stability is decreased.

  The liquid photosensitive adhesive of the present embodiment improves the film thickness uniformity after coating, thermocompression bonding after B-stage, low stress after thermosetting, and adhesion to the adherend ( E) A thermoplastic resin may be further contained.

  (E) It is preferable that Tg of a 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 ° C., the viscosity of the 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” of the component (E) means a main dispersion peak temperature when the component (E) is formed into a film. Specifically, for the film of component (E), using a viscoelasticity analyzer “RSA-2” (trade name) manufactured by Rheometrix, film thickness is 100 μm, heating rate is 5 ° C./min, frequency is 1 Hz, measurement temperature. The measurement is performed at −150 to 300 ° C., and the tan δ peak temperature near Tg is obtained as Tg.

  (E) It is preferable that the weight average molecular weight of a component is controlled within the range of 5000-500000. Furthermore, as for the weight average molecular weight of (E) component, it is more preferable that it is 10,000 to 300,000 at 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.

  Examples of the component (E) include polyester resins, polyether resins, polyimide resins, polyamide resins, polyamideimide resins, polyetherimide resins, polyurethane resins, polyurethaneimide resins, polyurethaneamideimide resins, siloxane polyimide resins, and polyesterimide resins. In addition to these copolymers and their precursors (polyamide acid, etc.), polybenzoxazole resin, phenoxy resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, polyester resin, polyether resin, polycarbonate resin, poly Examples thereof include ether ketone resins, (meth) acrylic copolymers having a weight average molecular weight of 10,000 to 1,000,000, novolac resins, and phenol resins. These can be used individually by 1 type or in combination of 2 or more types. In addition, the main chain and / or side chain of these resins may be provided with a glycol group such as ethylene glycol or propylene glycol, a carboxyl group, and / or a hydroxyl group.

  Among these, from the viewpoint of high temperature adhesiveness and heat resistance, the component (E) is preferably a resin having an imide group. Examples of the resin having an imide group include a polyimide resin, a polyamideimide resin, a polyetherimide resin, a polyurethaneimide resin, a polyurethaneamideimide resin, a siloxane polyimide resin, a polyesterimide resin, a copolymer thereof, and a monomer having an imide group. These polymers are mentioned.

  The polyimide resin and / or the polyamideimide resin can be obtained, for example, 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. In addition, in order to suppress the fall of the various characteristics of a resin composition, it is preferable that said tetracarboxylic dianhydride is what recrystallized and refined with acetic anhydride.

  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 amine-terminated polyimide oligomer tends to increase, the weight average molecular weight of the polyimide resin decreases, and various properties including the heat resistance of the resin composition tend to be insufficient. On the other hand, when the total of diamines is less than 0.5 mol with respect to 1.0 mol of tetracarboxylic dianhydride, the amount of acid-terminated polyimide resin oligomer tends to increase, and polyimide resin and / or polyamideimide The weight average molecular weight of the resin tends to be low, and various properties including the heat resistance of the resin composition tend to be insufficient.

  The polyimide resin and / or the polyamideimide resin can be obtained by dehydrating and ring-closing the reaction product (polyamide 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.

  Examples of the tetracarboxylic dianhydride used as a raw material for the polyimide resin include pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in that the linear expansion coefficient can be reduced. 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetracarboxylic Acid dianhydrides having a biphenyl skeleton such as acid dianhydrides, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3 Acid dianhydrides having a naphthyl skeleton such as 1,6,7-naphthalene tetracarboxylic dianhydride and 1,2,4,5-naphthalene tetracarboxylic dianhydride are preferably used. In addition, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, Acid dianhydrides having a benzophenone skeleton such as 3,3 ′, 4′-benzophenone tetracarboxylic dianhydride are preferably used. From the viewpoint of transparency, 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, 1,2 , 3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2,2] -oct-7 -Acid dianhydrides having an alicyclic skeleton such as ene-2,3,5,6-tetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 2,2-bis [4- (3,4-dicarboxy Phenyl) hexafluoropropane dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis ( An acid dianhydride having a fluoroalkyl group such as trimellitic anhydride is preferably used.

  Moreover, the tetracarboxylic dianhydride etc. which are represented by following General formula (1) from the transparency viewpoint with respect to 365 nm are used preferably. In the following general formula (1), a represents an integer of 2 to 20.

  The tetracarboxylic dianhydride represented by the general formula (1) can be synthesized from, for example, trimellitic anhydride monochloride and the corresponding diol, specifically 1,2- (ethylene) bis ( Trimellitate 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 (trimellitate anhydride), 1,16 (hexamethylene decamethylene) bis (trimellitate anhydride), 1,18 (octadecamethylene) bis (trimellitate anhydride) and the like. These compounds can lower Tg without impairing heat resistance.

  The tetracarboxylic dianhydride is represented by the following general formula (2) or (3) from the viewpoint of imparting good solubility in the component (A), transparency to 365 nm light, and thermocompression bonding. Tetracarboxylic dianhydride is preferred.

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

  The component (E) 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 general formula (4), (5), (6) or (7).

  Although it does not specifically limit as another diamine used as a raw material of the said polyimide resin, In order to adjust Tg and solubility of a polymer, the following diamine can be used. For example, o-phenylene diamine, m-phenylene diamine, p-phenylene diamine, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3) can improve heat resistance and adhesiveness. , 5-diisopropylphenyl) methane, 2,2-bis (3-aminophenyl) propane, 2,2 ′-(3,4′-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylene Bis (1-methylethylidene)) bisaniline, 3,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′-(1, - phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4-aminophenoxy phenyl) propane is preferably used. 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4, 4′-diaminodiphenyl ether methane, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, bis (4- (3-aminoenoxy) phenyl) sulfone, bis (4 -(4-Aminoenoxy) phenyl) sulfone, 3,3'-dihydroxy-4,4'-diaminobiphenyl is preferably used. 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, bis (4- (3- Aminoenoxy) phenyl) sulfide and bis (4- (4-aminoenoxy) phenyl) sulfide are preferably used. Moreover, as diamine which can reduce Tg, 1, 3-bis (aminomethyl) cyclohexane, aliphatic ether diamine represented by the following general formula (8), siloxane diamine represented by the following general formula (9) Etc.

一般式（８）中、Ｒ^１、Ｒ^２及びＲ^３は各々独立に、炭素数１〜１０のアルキレン基を示し、ｂは２〜８０の整数を示す。

In the general formula (8), 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.

一般式（９）中、Ｒ^４及びＲ^９は各々独立に、炭素数１〜５のアルキレン基又は置換基を有してもよいフェニレン基を示し、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は各々独立に、炭素数１〜５のアルキル基、フェニル基又はフェノキシ基を示し、ｄは１〜５の整数を示す。

In general formula (9), 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.

  Among the diamines, aliphatic ether diamines represented by the general formula (8) are preferable, and ethylene glycol and / or propylene glycol-based diamines are more preferable in terms of imparting compatibility with other components.

  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) polyetheramine D-230, D-400, D-2000 and other aliphatic diamines such as polyoxyalkylene diamine. These diamines are preferably 20 mol% or more of the total diamine, and are compatible with other components such as (A) radiation-polymerizable compounds and (C) thermosetting resins, and thermocompression bonding and high-temperature adhesion. It is more preferable that it is 50 mol% or more from the standpoint of achieving high compatibility with the properties.

  Moreover, as said diamine, the siloxane diamine represented by the said General formula (9) is preferable at the point which provides the adhesiveness and adhesiveness in room temperature.

  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.

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

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

  In addition, as described above, when determining the composition of the polyimide resin, it is preferable to design the Tg to be 150 ° C. or less. As the diamine that is the raw material of the polyimide resin, the general formula (8) It is particularly preferred to use the aliphatic ether diamine represented.

  By adding a monofunctional acid anhydride and / or a monofunctional amine such as a compound represented by the following general formula (10), (11) or (12) to the condensation reaction solution during the synthesis of the polyimide resin, Functional groups other than acid anhydrides or diamines can be introduced at the polymer terminals. Thereby, the molecular weight of the polymer can be lowered, the viscosity of the adhesive can be lowered, and the thermocompression bonding property can be improved.

  (E) The thermoplastic resin may have a functional group having a function of promoting the curing of an epoxy resin such as imidazole in its main chain and / or side chain. The imidazole-containing polyimide can be obtained, for example, by using a diamine group-containing diamine as shown in the following structural formula as a diamine component shown above. A polymer having such an imidazole in the side chain is preferable because compatibility and storage stability can be improved.

  From the point that the polyimide resin can be uniformly B-staged, the transmittance for 365 nm when molded to 30 μm is preferably 10% or more, and is 20% or more in that it can be B-staged at a lower exposure. It is more preferable. Such a polyimide resin is represented by, for example, an acid anhydride represented by the general formula (2), an aliphatic ether diamine represented by the general formula (8), and / or the general formula (9). It can be synthesized by reacting with siloxane diamine.

  In addition, as the thermoplastic resin (E), 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 adhesive composition. . Such a thermoplastic resin can be reacted by heating without using a solvent, and in an adhesive composition that does not apply the solvent as in the present invention, the solvent removal process is reduced, the residual solvent is reduced, and the reprecipitation process is performed. This is useful in terms of reduction. The liquid thermoplastic resin can be easily taken out from the reaction furnace. Examples of such a liquid thermoplastic resin include rubber-like polymers such as polybutadiene, acrylonitrile / butadiene oligomer, polyisoprene, and polybutene, polyolefins, acrylic polymers, silicone polymers, polyurethanes, polyimides, and polyamideimides. Of these, a polyimide resin is preferably used.

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

  (E) 0.1-50 mass% is preferable with respect to (A) component, and the content of a thermoplastic resin is 0.5-20 mass from a viewpoint of film formability, film thickness uniformity, and a viscosity raise suppression. % Is more preferable. If the content of the thermoplastic resin is less than 0.1% by mass, the effect of addition tends to be lost, and if it exceeds 50% by mass, the film thickness uniformity decreases due to undissolved or the like. It tends to rise and make thinning difficult.

  The liquid photosensitive adhesive of this embodiment is prohibited from polymerization of quinones, polyphenols, phenols, phosphites, sulfurs, etc. in order to impart storage stability, process adaptability or antioxidant properties. You may further add an agent or antioxidant in the range which does not impair sclerosis | hardenability.

  Moreover, the liquid photosensitive adhesive of this embodiment can also 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, Inorganic fillers such as aluminum oxide, aluminum nitride, crystalline silica, amorphous silica, boron nitride, titania, glass, iron oxide, and ceramics, and organic fillers such as carbon and rubber fillers are included. Regardless, it can be used without any particular restrictions.

  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, etc. to the adhesive, and the non-metallic inorganic filler has thermal conductivity, low thermal expansion, low hygroscopicity, etc. for the adhesive layer. It is added for the purpose of imparting, and the organic filler is added for the purpose of imparting toughness and the like to the adhesive layer.

  These metal fillers, inorganic fillers, or organic fillers can be used singly or in combination of two or more. Among them, metal fillers, inorganic fillers, or insulating fillers are preferable in terms of being able to impart conductivity, thermal conductivity, low moisture absorption characteristics, insulating properties, and the like required for adhesive materials for semiconductor devices, and inorganic fillers or insulating fillers. Among the fillers, silica filler is more preferable in that it has good dispersibility with respect to the adhesive and can impart a high adhesive force when heated.

  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 or the maximum particle size exceeds 30 μm, the effect of improving fracture toughness tends to be insufficient. Further, the lower limits of the average particle size and the maximum particle size are not particularly limited, but both are preferably 0.001 μm or more.

  Although content of the said filler is determined according to the characteristic or function to provide, it is preferable that it is 50 mass% or less with respect to the adhesive agent whole quantity containing a filler, 1-40 mass% is more preferable, 3-30 More preferred is mass%. 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. If the amount of filler is increased more than necessary, the viscosity tends to increase or the thermocompression bonding property tends to be impaired. Therefore, the filler content is preferably within the above range. The optimum filler content can be determined to balance the required properties. Mixing and kneading in the case of using a filler can be carried out by appropriately combining dispersers such as ordinary stirrers, raking machines, three rolls, and ball mills.

  Various coupling agents can be added to the liquid photosensitive adhesive of this embodiment in order to improve the interfacial bonding between different materials. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based. Among them, a silane-based coupling agent is preferable because of its high effect, and a thermosetting group such as an epoxy group, methacrylate, and / or acrylate. A compound having a radiation polymerizable group such as is more preferred.

  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. In particular, a silane coupling agent having a boiling point of 200 ° C. or higher and / or a decomposition temperature and having a thermosetting group such as an epoxy group and a radiation polymerizable group such as methacrylate and / or acrylate is most preferably used.

  It is preferable that the usage-amount of the said coupling agent shall be 0.01-20 mass parts with respect to 100 mass parts of adhesive whole quantity from the surface of the effect, heat resistance, and cost.

  In the liquid photosensitive adhesive of this embodiment, an ion scavenger may be further added 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 inorganic ion scavengers manufactured by Toa Gosei Co., Ltd., trade names, IXE-300 (antimony type), IXE-500 (bismuth type), IXE-600 (antimony and bismuth mixed type), IXE-700. (Magnesium and aluminum mixed system), IXE-800 (zirconium system), IXE-1100 (calcium system) and the like. These may be used alone or in combination of two or more. The amount of the ion scavenger used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the adhesive from the viewpoints of the effect of addition, heat resistance, cost, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

<Preparation of liquid photosensitive adhesive>
In the ratio (parts by mass) shown in Table 1 below, first, the thermosetting resin and the radiation-polymerizable compound were stirred in a four-necked separable flask installed in an oil bath while heating to 60 ° C. in a nitrogen atmosphere. , Dissolved. Next, a curing accelerator and a photopolymerization initiator were added to the obtained solution at a ratio (parts by mass) shown in Table 1 below, and the mixture was further stirred and dissolved. Thus, the liquid photosensitive adhesives of Preparation Examples 1 to 3 were obtained.

<Formation of photosensitive adhesive layer>
The obtained liquid photosensitive adhesive was apply | coated on the back surface of a 5-inch (PHI) silicon wafer using the spin coater (The Mikasa Co., Ltd. make, MS-200 (brand name)). When the state of the liquid photosensitive adhesive was visually confirmed, a uniform 20 μm thick photosensitive adhesive layer could be provided without fading.

<B-stage development of photosensitive adhesive layer>
A silicon wafer having a photosensitive adhesive layer formed therein is placed in an acrylic box, and a parallel exposure machine (manufactured by Mikasa Co., Ltd., Mask Aligner ML-210FM (trade name)) is used, with an oxygen concentration of 0%, 3%, The photosensitive adhesive layer was exposed to 1000 mJ / cm ² under 5%, 10%, and atmospheric conditions, respectively, and the photosensitive adhesive layer was made into B stage. The oxygen concentration was confirmed with an oxygen concentration meter installed in the acrylic box.

Next, on the surface of the B-staged photosensitive adhesive layer, Lami. Corporation. A dicing tape was laminated at a lamination temperature of 30 ° C. using Hotdog 12DX manufactured by Inc. Furthermore, a pressure sensitive DC tape SD-3000 manufactured by Hitachi Chemical Co., Ltd. was laminated on the dicing tape at 30 ° C.
About the laminated body obtained in this way, the peel strength (dicing tape 90 degree peeling peel strength) on the conditions of test piece width 10mm and test speed 300mm / min using Shimadzu Corporation AUTO GRAPH AGS-X 100N. By measuring, the surface tack force of the B-staged photosensitive adhesive layer was determined. The results are shown in Table 2.

Each symbol in Table 1 has the following meaning.
M-140: “Aronix M-140”, Toagosei Co., Ltd., 2- (1,2-cyclohexacarboximide) ethyl acrylate (imide group-containing monofunctional acrylate, 5% weight loss temperature: 200 ° C., 25 ° C. Viscosity at 450 mPa · s).
AMP-20GY: manufactured by Shin-Nakamura Chemical Co., Ltd., phenoxydiethylene glycol acrylate (monofunctional acrylate, 5% weight loss temperature: 175 ° C., viscosity at 25 ° C .: 16 mPa · s).
1032H60: JER Corporation, Japan Epoxy Resin Co., Ltd., α-2,3-epoxypropoxyphenyl-ω-hydropoly (n = 1-7) [2- (2,3-epoxypropoxy) benzylidene-2,3 -Epoxypropoxyphenylene] (tris (hydroxyphenyl) methane type solid epoxy resin.
I-651: Ciba Japan Co., Ltd., 2,2-dimethoxy-1,2-diphenylethane-1-one (5% weight loss temperature: 170 ° C., i-line extinction coefficient: 400 ml / gcm).
I-819: Ciba Japan KK, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (5% weight loss temperature) : 260 ° C., i-ray absorption coefficient: 8000 ml / gcm).
I-379EG: Ciba Japan Co., Ltd., 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-monophonyl) phenyl] -1-butanone.
1B2PZ: Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole.

  Any photosensitive adhesive layer formed from the liquid photosensitive adhesives of Preparation Examples 1 to 3 can sufficiently reduce the surface tack of the photosensitive adhesive layer by performing exposure at an oxygen concentration of 10% or less. It was.

  DESCRIPTION OF SYMBOLS 1 ... Semiconductor wafer, 2 ... Semiconductor chip, 4 ... Adhesive tape (back grind tape), 5 ... Photosensitive adhesive layer, 5a ... Adhesive layer, 6 ... Adhesive tape (dicing tape), 7 ... Support member, 8 ... Grinding device, 9 ... Exposure device, 10 ... Wafer ring, 11 ... Dicing blade, 12 ... Die bonding device, 14 ... Hot plate, 16 ... Wire, 17 ... Sealing material, 20 ... Container, 22, 24 ... Vent pipe, 26 ... Oxygen concentration meter, 100 ... Semiconductor device, S1 ... Circuit surface of semiconductor wafer, S2 ... Back surface of semiconductor wafer.

Claims (5)

On one side of the semiconductor wafer, a liquid adhesive containing (A) a radiation polymerizable compound, (B) a photopolymerization initiator, and (C) a thermosetting resin is applied to provide a photosensitive adhesive layer. Process,
A step of obtaining a semiconductor wafer with an adhesive layer by exposing the photosensitive adhesive layer in an atmosphere having an oxygen concentration of 10% or less to form a B-stage;
A method for producing a semiconductor wafer with an adhesive layer, comprising:   The manufacturing method of the semiconductor wafer with an adhesive layer of Claim 1 which exposes the said photosensitive adhesive bond layer in the atmosphere whose oxygen concentration is 5% or less. On one side of the semiconductor wafer, a liquid adhesive containing (A) a radiation polymerizable compound, (B) a photopolymerization initiator, and (C) a thermosetting resin is applied to provide a photosensitive adhesive layer. Process,
A step of obtaining a semiconductor wafer with an adhesive layer by exposing the photosensitive adhesive layer in an atmosphere having an oxygen concentration of 10% or less to form a B-stage;
Cutting the semiconductor wafer with an adhesive layer to obtain a semiconductor element with an adhesive layer;
Bonding the semiconductor element with an adhesive layer and another semiconductor element or a support member for mounting a semiconductor element by crimping the adhesive layer of the semiconductor element with the adhesive layer, and
A method for manufacturing a semiconductor device.   The method for manufacturing a semiconductor device according to claim 3, wherein the exposure of the photosensitive adhesive layer is performed in an atmosphere having an oxygen concentration of 5% or less.   A semiconductor device obtained by the method according to claim 3.

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