JP2021082650A - Dicing/die bonding integral film and manufacturing method thereof, and manufacturing method of semiconductor device - Google Patents

Abstract

To provide a dicing/die bonding integral film comprising a pressure-sensitive adhesive layer having excellent pickup performance.SOLUTION: A film 10 comprise: a substrate layer 1; a pressure-sensitive adhesive layer 3 having a first surface F1 facing the substrate layer 1 and a second surface F2 on the opposite side thereof; and an adhesive layer 5 provided so as to cover the central portion of the second surface F2. The pressure-sensitive adhesive layer 3 includes a first region 3a including a region corresponding to the wafer attachment position in the adhesive layer 5 and a second region 3b located so as to surround the first region 3a, the first region 3a is a region in which the tack strength is reduced as compared with the second region 3b. A difference between the tack strength of the first region 3a of the pressure-sensitive adhesive layer 3 to the adhesive layer 5 and the tack strength of the second region 3b of the pressure-sensitive adhesive layer 3 to the adhesive layer 5 measured under a predetermined condition is 6.5 to 9.0 N/25 mm.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a dicing / die bonding integrated film and a method for manufacturing the same, and a method for manufacturing a semiconductor device.

The semiconductor device is manufactured through the following steps. First, the dicing step is carried out with the adhesive film for dicing attached to the wafer. After that, an expanding step, a pick-up step, a mounting step, a die bonding step and the like are carried out.

In the manufacturing process of semiconductor devices, a film called a dicing / die bonding integrated film is used. This film has a structure in which a base material layer, an adhesive layer, and an adhesive layer are laminated in this order, and is used, for example, as follows. First, the surface on the adhesive layer side is attached to the wafer, and the wafer is diced with the wafer fixed by the dicing ring. As a result, the wafer is fragmented into a plurality of chips. Subsequently, the adhesive layer is weakened by irradiating the adhesive layer with active energy rays to weaken the adhesive force of the adhesive layer against the adhesive layer, and then the adhesive is attached to the chip together with the adhesive piece in which the adhesive layer is individualized. Pick up from the layer. After that, the semiconductor device is manufactured through a step of mounting the chip on a substrate or the like via an adhesive piece. A laminate composed of a chip obtained through a dicing step and an adhesive piece attached to the chip is called a DAF (Die Attach Film).

As described above, the pressure-sensitive adhesive layer (dicing film) whose adhesive strength is weakened by irradiation with active energy rays is called an active energy ray-curable type. On the other hand, a pressure-sensitive adhesive layer in which the adhesive strength remains constant without being irradiated with active energy rays in the manufacturing process of a semiconductor device is called a pressure-sensitive type. The dicing / die bonding integrated film provided with the pressure-sensitive adhesive layer does not require a process of irradiating active energy rays for the user (mainly a semiconductor device manufacturer), and does not require equipment for this purpose. There is a merit that there is. Patent Document 1 can be said to be an active energy ray-curable type in that the pressure-sensitive adhesive layer contains a component that is cured by active energy rays, while only a predetermined portion of the pressure-sensitive adhesive layer is preliminarily irradiated with active energy rays. Therefore, a dicing / die bonding integrated film that can be said to be pressure-sensitive in that the user does not need to irradiate active energy rays in the manufacturing process of the semiconductor device is disclosed.

Japanese Patent No. 4443962

In general, the pressure-sensitive adhesive layer of a dicing-die bonding integrated film is required to have a low adhesive force between the pressure-sensitive adhesive layer and the adhesive layer. If the adhesive strength is too high, a pickup error may occur in the chip pick-up process, and the yield may decrease. However, the present inventors have reduced the size of the chip to be produced by dicing (for example, an area of 0.1 to 9 mm ² in a plan view), and the pick-up property of the chip is between the adhesive layer and the adhesive layer. It has been found that the adhesive force is not necessarily dominant, and the peeling of the edge of the chip from the pressure-sensitive adhesive layer (hereinafter referred to as "edge peeling") is the dominant factor of the pick-up property. That is, the pick-up property of a small chip is mainly dominated by the edge peeling strength of the chip with adhesive piece, and once the edge peeling occurs by pushing up with a pin, the interface peeling between the adhesive layer and the adhesive layer is smooth thereafter. It is presumed that it will progress to.

As an influencing factor of the edge peeling strength, for example, curing shrinkage of the pressure-sensitive adhesive layer can be mentioned. Usually, after the dicing step, burrs (cutting chips) generated by mixing the adhesive layer, the adhesive layer, the wafer and the like are generated in the dicing line. If the pressure-sensitive adhesive layer is of the active energy ray-curable type, the pressure-sensitive adhesive layer may be cured together with burrs (cutting chips) by irradiation with the active energy rays, and the edge peeling strength may be significantly increased. If the pressure-sensitive adhesive layer is cured in advance before the dicing process, there is no such effect because it is not necessary to carry out the step of irradiating the active energy rays, but at the interface of the adhesive layer due to curing shrinkage of the pressure-sensitive adhesive layer. The anchor effect may increase the edge peeling strength. As a result of diligent studies on the curing shrinkage of the pressure-sensitive adhesive layer by the present inventors, the magnitude of the curing shrinkage tends to increase as the difference in the adhesive strength of the pressure-sensitive adhesive layer before and after irradiation of the adhesive layer with active energy rays increases. I found that there is. Therefore, the present inventors discuss the difference between the adhesive force of the pressure-sensitive adhesive layer before irradiation with the active energy ray and the adhesive force of the pressure-sensitive adhesive layer after irradiation with the active energy ray (in other words, the non-irradiated portion of the active energy ray). It is considered that the edge peeling strength can be reduced by adjusting the adhesive force of the adhesive layer and the adhesive force of the adhesive layer of the irradiated portion of the active energy ray), and the dying has excellent pick-up property. Worked on the development of die bonding integrated film.

The present disclosure is applicable to a manufacturing process of a semiconductor device including a step of fragmenting a wafer into a plurality of small chips (area 0.1 ^{to 9 mm 2), and includes an adhesive layer having excellent pick-up property.} The main purpose is to provide a dicing / die bonding integrated film and a method for producing the same.

One aspect of the present disclosure relates to a dicing / die bonding integrated film. This film comprises a base material layer, a pressure-sensitive adhesive layer made of an active energy ray-curable pressure-sensitive adhesive having a first surface facing the base material layer and a second surface opposite to the first surface, and a first. The adhesive layer includes an adhesive layer provided so as to cover the central portion of the two surfaces, and the adhesive layer includes a first region including at least a region corresponding to a bonding position of a wafer in the adhesive layer, and a first region. The first region has a second region located so as to surround the area, and the first region is a region in which the adhesive strength is reduced as compared with the second region by irradiation with active energy rays, and the temperature is 23 ° C. The adhesive force of the first region of the adhesive layer with respect to the adhesive layer, which is measured under the conditions of a peeling angle of 30 ° and a peeling speed of 60 mm / min, is F1 (N / 25 mm), a peeling angle of 30 ° at a temperature of 23 ° C. When the adhesive force of the second region of the adhesive layer with respect to the adhesive layer, which is measured under the condition of a peeling speed of 60 mm / min, is F2 (N / 25 mm), the difference (F2-F1) between F2 and F1 is. , 6.5-9.0 N / 25 mm. This film is applied to a semiconductor device manufacturing process that includes the step of fragmenting a wafer into a plurality of chips having an area of 0.1 to 9 mm ^2.

According to the dicing / die bonding integrated film, the curing shrinkage of the adhesive layer can be suppressed and the edge peeling strength can be reduced, so that the wafer can be made into a plurality of small chips (area 0.1 ^{to 9 mm 2} ). It can be applied to a manufacturing process of a semiconductor device including a step of individualizing, and excellent pick-up property from an adhesive layer can be achieved.

The difference between F2 and F1 (F2-F1) may be 7.0 to 9.0 N / 25 mm.

F1 (adhesive strength of the first region to the adhesive layer, measured at a temperature of 23 ° C. under conditions of a peeling angle of 30 ° and a peeling speed of 60 mm / min) can achieve better pick-up from the adhesive layer. From the viewpoint, it may be 1.1 to 4.5 N / 25 mm or 1.1 to 3.0 N / 25 mm.

The adhesive force of the second region of the pressure-sensitive adhesive layer on the stainless steel substrate may be 0.2 N / 25 mm or more from the viewpoint of suppressing ring peeling in the dicing step. This adhesive force means the peel strength measured under the conditions of a peeling angle of 90 ° and a peeling speed of 50 mm / min at a temperature of 23 ° C.

The active energy ray-curable pressure-sensitive adhesive may contain a (meth) acrylic resin having a functional group capable of chain polymerization. When such a (meth) acrylic resin is contained, the functional group may be at least one selected from an acryloyl group and a methacryloyl group, and the content of the functional group in the (meth) acrylic resin is 0.1. It may be ~ 1.2 mmol / g.

The active energy ray-curable pressure-sensitive adhesive may further contain a cross-linking agent. When such a cross-linking agent is further contained, the content of the cross-linking agent with respect to the total mass of the active energy ray-curable pressure-sensitive adhesive may be 0.1 to 15% by mass. The cross-linking agent may be a reaction product of a polyfunctional isocyanate having two or more isocyanate groups in one molecule and a polyhydric alcohol having three or more hydroxy groups in one molecule.

The irradiation amount of the active energy ray may be 10 to ^{1000 mJ / cm 2.}

The adhesive layer may consist of an adhesive composition containing a reactive group-containing (meth) acrylic copolymer, a curing accelerator, and a filler.

One aspect of the present disclosure relates to a method for producing a dicing / die bonding integrated film. This production method includes a step of producing a laminate containing an adhesive layer made of an active energy ray-curable adhesive and an adhesive layer formed on the surface of the adhesive layer on the surface of the base material layer. In this order, a step of irradiating a region to be a first region of the pressure-sensitive adhesive layer contained in the laminated body with active energy rays is provided.

One aspect of the present disclosure relates to a method of manufacturing a semiconductor device. This manufacturing method includes the step of preparing the dicing / die bonding integrated film, attaching the wafer to the adhesive layer of the dicing / die bonding integrated film, and dicing the second surface of the adhesive layer. The process of attaching the ring, the process of separating the wafer into a plurality of chips, the process of picking up the chip from the adhesive layer together with the adhesive piece in which the adhesive layer is individualized, and the process of picking up the chip from the adhesive layer, and via the adhesive piece The chip is mounted on a substrate or another chip.

That is, in this production method, a pressure-sensitive adhesive layer made of an active energy ray-curable pressure-sensitive adhesive having a base material layer, a first surface facing the base material layer, and a second surface opposite to the first surface. A step of preparing a dicing / die bonding integrated film including an adhesive layer provided so as to cover the central portion of the second surface of the adhesive layer, and an adhesive layer of the dicing / die bonding integrated film. A step of sticking a wafer on the surface and a dicing ring on the second surface of the adhesive layer, a step of separating the wafer into a plurality of chips, and an adhesion in which the adhesive layer is separated into individual pieces. The adhesive layer includes a step of picking up the chip from the adhesive layer together with the adhesive piece and a step of mounting the chip on the substrate or another chip via the adhesive piece, and the adhesive layer is attached with a wafer in the adhesive layer. It has a first region corresponding to the region to be bonded and a second region corresponding to the region to which the dicing ring is attached, and the first region is compared with the second region by irradiation with active energy rays. The adhesive strength of the first region of the adhesive layer with respect to the adhesive layer, which is a region in which the adhesive strength is reduced and is measured under the conditions of a peeling angle of 30 ° and a peeling speed of 60 mm / min at a temperature of 23 ° C., is set to F1 ( N / 25 mm), the adhesive strength of the second region of the adhesive layer to the adhesive layer measured under the conditions of a peeling angle of 30 ° and a peeling speed of 60 mm / min at a temperature of 23 ° C. was defined as F2 (N / 25 mm). When, the difference between F2 and F1 (F2-F1) is 6.5 to 9.0 N / 25 mm.

According to the present disclosure, an adhesive layer that can be applied to a manufacturing process of a semiconductor device including a step of individualizing a wafer into a plurality of small chips (area 0.1 ^{to 9 mm 2) and has excellent pick-up property.} A dicing / die bonding integrated film comprising the above and a method for producing the same are provided. Further, according to the present disclosure, there is provided a method for manufacturing a semiconductor device using such a dicing / die bonding integrated film.

FIG. 1A is a plan view showing an embodiment of a dicing / diebonding integrated film, and FIG. 1B is a schematic cross-sectional view taken along the line BB shown in FIG. 1A. is there. FIG. 2 is a schematic view showing a state in which a dicing ring is attached to the peripheral edge of the adhesive layer of the dicing / die bonding integrated film and a wafer is attached to the surface of the adhesive layer. FIG. 3 is a cross-sectional view schematically showing how the 30 ° peel strength of the pressure-sensitive adhesive layer with respect to the pressure-sensitive adhesive layer is measured. FIG. 4 is a schematic cross-sectional view of an embodiment of a semiconductor device. 5 (a), 5 (b), 5 (c), and 5 (d) are cross-sectional views schematically showing a process of manufacturing DAF (a laminate of chips and adhesive pieces). .. FIG. 6 is a cross-sectional view schematically showing a process of manufacturing the semiconductor device shown in FIG. FIG. 7 is a cross-sectional view schematically showing a process of manufacturing the semiconductor device shown in FIG. FIG. 8 is a cross-sectional view schematically showing a process of manufacturing the semiconductor device shown in FIG. 9 (a), 9 (b), and 9 (c) are cross-sectional views schematically showing a step of measuring the edge peeling strength. FIG. 10 is a graph showing an example of the relationship between the displacement (mm) due to pushing and the pushing force (N). FIG. 11 is a plan view schematically showing a state in which a mark is added at a position corresponding to the central portion of the chip to be measured.

Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings. In the following description, the same or corresponding parts will be designated by the same reference numerals, and duplicate description will be omitted. The present invention is not limited to the following embodiments. As used herein, the term (meth) acrylic means acrylic or methacrylic, as well as other similar expressions such as (meth) acrylate.

<Dicing / die bonding integrated film>
FIG. 1A is a plan view showing a dicing / diebonding integrated film according to the present embodiment, and FIG. 1B is a schematic cross-sectional view taken along the line BB of FIG. The dicing / die bonding integrated film 10 (hereinafter, in some cases, simply referred to as “film 10”) is ^{a step of separating the wafer W into a plurality of chips having an area of 0.1 to 9 mm 2} (and subsequent pick-up). It can be used in a manufacturing process of a semiconductor device including a step) (see FIGS. 5 (c) and 5 (d)).

The film 10 is a pressure-sensitive adhesive layer 3 having a base material layer 1, a first surface F1 facing the base material layer 1, and a second surface F2 opposite to the first surface F1, and the pressure-sensitive adhesive layer 3. An adhesive layer 5 provided so as to cover the central portion of the second surface F2 is provided in this order. In the present embodiment, an embodiment in which one laminate of the pressure-sensitive adhesive layer 3 and the adhesive layer 5 is formed on the square base material layer 1 is illustrated, but the base material layer 1 has a predetermined length. The laminated body of the pressure-sensitive adhesive layer 3 and the adhesive layer 5 may be arranged at predetermined intervals so as to have a square (for example, 100 m or more) and line up in the longitudinal direction thereof.

(Adhesive layer)
The pressure-sensitive adhesive layer 3 has a first region 3a including at least a region Rw corresponding to a bonding position of the wafer W in the adhesive layer 5, and a second region 3b located so as to surround the first region 3a. .. The broken lines in FIGS. 1 (a) and 1 (b) indicate the boundary between the first region 3a and the second region 3b. The first region 3a and the second region 3b are composed of the same composition (active energy ray-curable pressure-sensitive adhesive) before irradiation with active energy rays. The first region 3a is a region in which the adhesive strength is reduced as compared with the second region 3b by being irradiated with the active energy rays. The second region 3b is a region to which the dicing ring DR is attached (see FIG. 2). The second region 3b is a region not irradiated with active energy rays and has a high adhesive force to the dicing ring DR. The active energy ray may be at least one selected from ultraviolet rays, electron beams, and visible rays, and may be ultraviolet rays. The irradiation amount of the active energy ray may be, for example, 10 to 1000 mJ / cm ² , 100 to 700 mJ / cm ² , or 200 to 500 mJ / cm ² .

The adhesive force of the second region 3b of the adhesive layer 3 to the adhesive layer 5 is F2 (N / 25 mm), and the adhesive force of the first region 3a of the adhesive layer 3 to the adhesive layer 5 is F1 (N / 25 mm). ), The difference (F2-F1) between F2 and F1 is 6.5 to 9.0 N / 25 mm, and may be 7.0 to 9.0 N / 25 mm. Here, F1 and F2 are 30 ° peel intensities measured under the conditions of a peeling angle of 30 ° and a peeling speed of 60 mm / min at a temperature of 23 ° C. FIG. 3 is a cross section schematically showing how the 30 ° peel strength of the adhesive layer 3 is measured with the adhesive layer 5 of the measurement sample (width 25 mm × length 100 mm) fixed to the support plate 80. It is a figure. FIG. 3 may be a measurement of F1. The second region 3b of the pressure-sensitive adhesive layer 3 is a region in the same state as the pressure-sensitive adhesive layer before irradiation with active energy rays, and can be said to be a region not irradiated with active energy rays. Therefore, F2 can be measured by replacing the pressure-sensitive adhesive layer 3 in FIG. 3 with a pressure-sensitive adhesive layer 3 that does not have the first region 3a. Since the state of the pressure-sensitive adhesive layer 3 having no first region 3a is the state before irradiating the pressure-sensitive adhesive layer with active energy rays, F2 is, for example, on the surface of the base material layer 1. Using a laminate containing an adhesive layer made of an active energy ray-curable pressure-sensitive adhesive and an adhesive layer 5 formed on the surface of the pressure-sensitive adhesive layer, the adhesive layer 5 is subjected to before irradiation with active energy rays. It can be determined by measuring the adhesive strength of the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer 3 that does not have the first region 3a). (F2-F1) to by such a range suppresses the cure shrinkage of the adhesive layer since it is possible to reduce edge delamination strength, a small chip of a plurality of wafers (area 0.1～9Mm ² It can be applied to a manufacturing process of a semiconductor device including a step of individualizing into (), and excellent pick-up property from the pressure-sensitive adhesive layer 3 can be achieved. (F2-F1) may be 6.6 N / 25 mm or more, 6.8 N / 25 mm or more, 7.0 N / 25 mm or more, or 7.2 N / 25 mm or more, and 8.8 N / 25 mm or less, 8. It may be 6N / 25mm or less, 8.4N / 25mm or less, or 8.2N / 25mm or less.

As described above, the film 10 can also be suitably used in a manufacturing process of a semiconductor device including a step of fragmenting ^{a wafer into a plurality of small chips having an area of 0.1 to 9 mm 2 (and a step of picking up the wafer thereafter).} it can. The present inventors have focused on the difference between the pickup behavior of a small chip having a size of 3 mm × 3 mm or less (area 9 mm ² or less) and the pickup behavior of a large chip having a size of, for example, about 8 mm × 6 mm. As a result, the difference (F2-F1) between the adhesive force of the second region 3b of the adhesive layer 3 with respect to the adhesive layer 5 and the adhesive force of the first region 3a of the adhesive layer 3 with respect to the adhesive layer 5 is 6 It was specified as .5-9.0 N / 25 mm. The present inventors have previously found that edge peeling is a dominant factor in pick-up property in small chips, and that the main cause of an increase in edge peeling strength is hardening shrinkage (F2-F1). It was further found that by setting the thickness to 6.5 to 9.0 N / 25 mm, curing shrinkage can be suppressed and excellent pick-up property from the pressure-sensitive adhesive layer 3 can be achieved. This makes it possible to manufacture a semiconductor device with a sufficiently high yield by using the film 10.

The adhesive force (F1) of the first region 3a of the pressure-sensitive adhesive layer 3 to the adhesive layer 5 may be, for example, 1.1 to 4.5 N / 25 mm or 1.1 to 3.0 N / 25 mm. F1 may be 1.2N / 25mm or more, 1.5N / 25mm or more, or 2.0N / 25mm or more, 4.0N / 25mm or less, 3.7N / 25mm or less, 3.5N / 25mm or less. It may be 3.2 N / 25 mm or less, or 3.0 N / 25 mm or less.

The first region 3a having an adhesive force in the above range with respect to the adhesive layer 5 is formed by irradiation with active energy rays, and can be said to be an active energy ray irradiation region. The present inventors have also found that reducing the adhesive force of the pressure-sensitive adhesive layer by irradiation with active energy rays affects the peeling of the edge portion of the DAF. That is, if the adhesive strength of the first region 3a is excessively reduced by irradiation with active energy rays, the 30 ° peel strength of the first region 3a with respect to the adhesive layer 5 becomes low, but the pick-up target is small. In the case of a chip, the edge portion of the DAF tends to be difficult to peel off, and the chip is excessively deformed, and cracks or pickup mistakes are likely to occur. It can also be said that the lower limit of the adhesive force of the first region 3a with respect to the adhesive layer 5 (for example, 1.1 N / 25 mm) does not excessively reduce the adhesive force before irradiation with the active energy ray. This makes it easier for the edge portion of the DAF to peel off even with a small chip. On the other hand, if the adhesive force of the first region 3a to the adhesive layer 5 is excessively high, the pick-up property tends to decrease. The upper limit of the adhesive force of the first region 3a with respect to the adhesive layer 5 (for example, 4.5 N / 25 mm) reduces the adhesive force before irradiation with the active energy ray to the extent that excellent pick-up property is exhibited. It can be said that it is a thing.

The adhesive force (F2) of the second region 3b of the pressure-sensitive adhesive layer 3 to the adhesive layer 5 may be, for example, 8.0 to 11.5 N / 25 mm. F2 may be 8.5 N / 25 mm or more, 9.0 N / 25 mm or more, or 9.5 N / 25 mm or more, 11.0 N / 25 mm or less, 10.8 N / 25 mm or less, or 10.5 N / 25 mm. It may be as follows.

In the present embodiment, for example, the content of chain-growth-polymerizable functional groups in the (meth) acrylic resin (content of the functional group-introduced compound), the content of the cross-linking agent in the pressure-sensitive adhesive layer, and the irradiation amount of active energy rays. By adjusting, or by adding other resins (acrylic monomer or oligomer, urethane monomer or oligomer, etc.) or tackifier (tackfire, etc.), F1, F2, and (F2-F1). ) Can be adjusted.

The adhesive strength of the second region 3b of the pressure-sensitive adhesive layer 3 to the stainless steel substrate may be 0.2 N / 25 mm or more. This adhesive strength is a 90 ° peel strength measured under the conditions of a peeling angle of 90 ° and a peeling speed of 50 mm / min at a temperature of 23 ° C. When this adhesive force is 0.2 N / 25 mm or more, peeling of the ring during dicing can be sufficiently suppressed. The adhesive strength of the second region 3b of the pressure-sensitive adhesive layer 3 to the stainless steel substrate may be 0.25 N / 25 mm or more or 0.3 N / 25 mm or more, 2.0 N / 25 mm or less, 1.0 N / 25 mm or less. , 0.8N / 25mm or less, or 0.6N / 25mm or less.

The pressure-sensitive adhesive layer before irradiation with the active energy ray comprises, for example, an active energy ray-curable pressure-sensitive adhesive containing a (meth) acrylic resin, a photopolymerization initiator, and a cross-linking agent. The second region 3b, which is not irradiated with the active energy rays, may have the same composition as the pressure-sensitive adhesive layer before the irradiation with the active energy rays. Hereinafter, the components contained in the active energy ray-curable pressure-sensitive adhesive will be described in detail.

[(Meta) acrylic resin]
The active energy ray-curable pressure-sensitive adhesive may contain a (meth) acrylic resin having a functional group capable of chain polymerization. When such a (meth) acrylic resin is contained, the functional group may be at least one selected from an acryloyl group and a methacryloyl group. The content of the functional group in the (meth) acrylic resin may be 0.1 to 1.2 mmol / g. The content of the functional group in the (meth) acrylic resin may be 0.2 mmol / g or more or 0.3 mmol / g or more, 1.0 mmol / g or less, 0.8 mmol / g or less, 0.7 mmol. It may be / g or less, 0.6 mmol / g or less, or 0.5 mmol / g or less. When the content of the functional group is 0.1 mmol / g or more, it tends to easily form a region (first region 3a) in which the adhesive strength is appropriately reduced by irradiation with active energy rays, while 1. When it is 2 mmol / g or less, it tends to be easy to achieve excellent pick-up property.

The (meth) acrylic resin can be obtained by synthesizing it by a known method. Examples of the synthesis method include a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, a massive polymerization method, a precipitation polymerization method, a vapor phase polymerization method, a plasma polymerization method, and a supercritical polymerization method. The types of polymerization reactions include radical polymerization, cationic polymerization, anionic polymerization, living radical polymerization, living cationic polymerization, living anionic polymerization, coordination polymerization, immodal polymerization, etc., as well as ATRP (atomic transfer radical polymerization) and RAFT (Atomic transfer radical polymerization). Techniques such as reversible addition cleavage chain transfer polymerization) can also be mentioned. Among these, the synthesis by radical polymerization using the solution polymerization method has good economic efficiency, high reaction rate, ease of polymerization control, etc., and can be blended by using the resin solution obtained by polymerization as it is. It has advantages such as.

Here, a method for synthesizing a (meth) acrylic resin will be described in detail by taking as an example a method of obtaining a (meth) acrylic resin by radical polymerization using a solution polymerization method.

The monomer used in synthesizing the (meth) acrylic resin is not particularly limited as long as it has one (meth) acryloyl group in one molecule. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, butoxyethyl (meth) acrylate, and isoamyl (meth) acrylate. , Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl heptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) Acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol ( Aliphatic (meth) acrylates such as meta) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, mono (2- (meth) acryloyloxyethyl) succinate; cyclopentyl (meth) acrylate, cyclohexyl (meth) Meta) acrylate, cyclopentyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, mono (2- (meth) acryloyloxyethyl) tetrahydrophthalate, mono ( Alicyclic (meth) acrylates such as 2- (meth) acryloyloxyethyl) hexahydrophthalate; benzyl (meth) acrylate, phenyl (meth) acrylate, o-biphenyl (meth) acrylate, 1-naphthyl (meth) acrylate , 2-naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, 1-naphthoxyethyl (meth) acrylate, 2-naphthoxyethyl (meth) acrylate ) Acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydro Xi-3- (o-phenylphenoxy) propyl (meth) acrylate, 2-hydroxy-3- (1-naphthoxy) propyl (meth) acrylate, 2-hydroxy-3- (2-naphthoxy) propyl (meth) acrylate, etc. Aromatic (meth) acrylate; 2-tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, 2- (meth) acryloyloxyethyl-N-carbazole, etc. Meta) acrylate, these caprolactone modified products, ω-carboxy-polycaprolactone mono (meth) acrylate, glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, α-propyl glycidyl (meth) acrylate, α-butyl glycidyl (Meta) acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, 2-propylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxyheptyl ( Meta) acrylate, α-ethyl-6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl Compounds having an ethylenically unsaturated group such as ether and an epoxy group; (2-ethyl-2-oxetanyl) methyl (meth) acrylate, (2-methyl-2-oxetanyl) methyl (meth) acrylate, 2- (2) -Ethyl-2-oxetanyl) ethyl (meth) acrylate, 2- (2-methyl-2-oxetanyl) ethyl (meth) acrylate, 3- (2-ethyl-2-oxetanyl) propyl (meth) acrylate, 3- ( A compound having an ethylenically unsaturated group such as 2-methyl-2-oxetanyl) propyl (meth) acrylate and an oxetanyl group; having an ethylenically unsaturated group such as 2- (meth) acryloyloxyethyl isocyanate and an isocyanate group. Compounds: 2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate Examples of compounds having an ethylenically unsaturated group and a hydroxyl group such as Be done. The desired (meth) acrylic resin can be obtained by appropriately combining these.

Even if the (meth) acrylic resin has at least one functional group selected from a hydroxyl group, a glycidyl group (epoxide group), an amino group and the like as a reaction point with a functional group-introducing compound or a cross-linking agent described later. Good. Examples of the monomer for synthesizing the (meth) acrylic resin having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 3-chloro. Examples thereof include compounds having an ethylenically unsaturated group and a hydroxyl group such as -2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate. These may be used alone or in combination of two or more.

Examples of the monomer for synthesizing a (meth) acrylic resin having a glycidyl group include glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, α-propyl glycidyl (meth) acrylate, and α-butyl glycidyl (meth). Acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, 2-propylglycidyl (meth) acrylate, 3,4-epoxide butyl (meth) acrylate, 3,4-epoxide heptyl (meth) acrylate , Α-Ethyl-6,7-epoxyheptyl (meth) acrylate, 3,4-epoxidecyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. Examples thereof include compounds having an ethylenically unsaturated group and an epoxy group. These may be used alone or in combination of two or more.

The (meth) acrylic resin synthesized from these monomers contains a functional group capable of chain polymerization. The chain-growthable functional group is, for example, at least one selected from an acryloyl group and a methacryloyl group. The functional group capable of chain polymerization is, for example, a (meth) acrylic resin having at least one functional group selected from a hydroxyl group, a glycidyl group (epoxide group), an amino group and the like synthesized as described above, and the following. By reacting a compound (functional group-introduced compound), it can be introduced into the (meth) acrylic resin. Specific examples of the functional group-introduced compound include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzylisocyanate, methacryloylisocyanate, allylisocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate; diisocyanate compound. Alternatively, an acryloyl monoisocyanate compound obtained by reacting a polyisocyanate compound with hydroxyethyl (meth) acrylate or 4-hydroxybutylethyl (meth) acrylate; a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth). Examples thereof include an acryloyl monoisocyanate compound obtained by reacting with acrylate. These may be used alone or in combination of two or more. Among these, the functional group-introduced compound may be 2-methacryloyloxyethyl isocyanate.

[Photopolymerization initiator]
The photopolymerization initiator is not particularly limited as long as it generates an active species capable of chain polymerization by irradiating with active energy rays. The active energy ray may be at least one selected from ultraviolet rays, electron beams, and visible rays, and may be ultraviolet rays. Examples of the photopolymerization initiator include a photoradical polymerization initiator. Here, the chain-growth-capable active species means one in which the polymerization reaction is initiated by reacting with a chain-polymerizable functional group.

Examples of the photoradical polymerization initiator include benzoinketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one; 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1-phenylpropane. Α-Hydroxyketones such as -1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one; 2-benzyl-2-dimethylamino- Α-Aminoketones such as 1- (4-morpholinophenyl) -butane-1-one, 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; 1- [4- (Phenylthio) phenyl] oxym ester such as -1,2-octadion-2- (benzoyl) oxime; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) Phenyl oxides such as -2,4,4-trimethylpentylphosphenyl oxide, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o) -Chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5- 2,4,5-Triarylimidazole dimer such as diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer; benzophenone, N, N, N', N' Phenylphenone compounds such as -tetramethyl-4,4'-diaminobenzophenone, N, N, N', N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone; 2-ethyl Anthraquinone, phenanthrenquinone, 2-tert-butyl anthraquinone, octamethyl anthraquinone, 1,2-benz anthraquinone, 2,3-benz anthraquinone, 2-phenyl anthraquinone, 2,3-diphenyl anthraquinone, 1-chloroanthraquinone, 2-methyl Kinone compounds such as anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin methyl ether, benzoin ethyl ether, benzoin phenyl A Benzoin ethers such as tell; benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin; benzyl compounds such as benzyldimethylketal; aclysines such as 9-phenylaclysine and 1,7-bis (9,9'-acridinylheptane). Compounds: N-phenylglycine, coumarin and the like.

The content of the photopolymerization initiator in the active energy ray-curable pressure-sensitive adhesive is 0.1 to 30 parts by mass, 0.3 to 10 parts by mass, or 0.3 to 10 parts by mass with respect to 100 parts by mass of the content of the (meth) acrylic resin. , 0.5 to 5 parts by mass. When the content of the photopolymerization initiator is 0.1 parts by mass or more, the pressure-sensitive adhesive layer is sufficiently cured after irradiation with active energy rays, and pick-up defects tend to be less likely to occur. When the content of the photopolymerization initiator is 30 parts by mass or less, contamination on the adhesive layer (transfer of the photopolymerization initiator to the adhesive layer) tends to be prevented.

[Crosslinking agent]
The cross-linking agent is used, for example, for the purpose of controlling the elastic modulus and / or the adhesiveness of the pressure-sensitive adhesive layer. The cross-linking agent may be a compound having two or more functional groups in one molecule capable of reacting with at least one functional group selected from the hydroxyl group, glycidyl group, amino group and the like possessed by the (meth) acrylic resin. Examples of the bond formed by the reaction between the cross-linking agent and the (meth) acrylic resin include an ester bond, an ether bond, an amide bond, an imide bond, a urethane bond, and a urea bond.

In this embodiment, the cross-linking agent may be, for example, a polyfunctional isocyanate having two or more isocyanate groups in one molecule. When such a polyfunctional isocyanate is used, it can easily react with the hydroxyl group, glycidyl group, amino group and the like contained in the (meth) acrylic resin to form a strong crosslinked structure.

Examples of the polyfunctional isocyanate having two or more isocyanate groups in one molecule include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylene diisocyanate. , Diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'- Examples thereof include isocyanate compounds such as diisocyanate and lysocyanate isocyanate.

The cross-linking agent may be a reaction product (isocyanate group-containing oligomer) of a polyfunctional isocyanate and a polyhydric alcohol having two or more hydroxy groups in one molecule. Examples of polyhydric alcohols having two or more hydroxy groups in one molecule include ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, 1,8-octanediol, and 1,9-nonanediol. 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, glycerin, trimethylrolpropane, pentaerythritol, dipentaerythritol, 1,4-cyclohexanediol, 1,3-cyclohexanediol and the like. Be done.

Among these, the cross-linking agent is a reaction product (isocyanate group-containing oligomer) of a polyfunctional isocyanate having two or more isocyanate groups in one molecule and a polyhydric alcohol having three or more hydroxy groups in one molecule. ) May be. By using such an isocyanate group-containing oligomer as a cross-linking agent, the pressure-sensitive adhesive layer 3 forms a dense cross-linked structure, which sufficiently suppresses the pressure-sensitive adhesive from adhering to the adhesive layer 5 in the pick-up step. Tend to be able to.

The content of the cross-linking agent in the active energy ray-curable pressure-sensitive adhesive can be appropriately set according to the cohesive force required for the pressure-sensitive adhesive layer, the elongation at break, the adhesion to the adhesive layer, and the like. Specifically, the content of the cross-linking agent is, for example, 3 to 30 parts by mass, 4 to 15 parts by mass, or 7 to 10 parts by mass with respect to 100 parts by mass of the content of the (meth) acrylic resin. You can. By setting the content of the cross-linking agent in the above range, it is possible to achieve both the characteristics required for the pressure-sensitive adhesive layer in the dicing step and the characteristics required for the pressure-sensitive adhesive layer in the die bonding step in a well-balanced manner, and it is excellent. Pick-up property can also be achieved.

If the content of the cross-linking agent is 3 parts by mass or more with respect to 100 parts by mass of the content of the (meth) acrylic resin, the formation of the cross-linked structure is unlikely to be insufficient, and the interface adhesion with the adhesive layer is likely to occur in the pick-up process. The force is sufficiently reduced and defects tend to be less likely to occur during pickup. On the other hand, when the content of the cross-linking agent is 30 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic resin content, the pressure-sensitive adhesive layer is unlikely to become excessively hard, and the chips tend to be difficult to peel off in the expanding step. It is in.

The content of the cross-linking agent with respect to the total mass of the active energy ray-curable pressure-sensitive adhesive may be, for example, 0.1 to 15% by mass, 3 to 15% by mass, or 5 to 15% by mass. When the content of the cross-linking agent is 0.1% by mass or more, it is easy to form a region (first region 3a) in which the adhesive strength is appropriately reduced by irradiation with active energy rays, while the content is 15% by mass or less. By being there, it tends to be easy to achieve excellent pick-up performance.

The thickness of the pressure-sensitive adhesive layer 3 may be appropriately set according to the conditions of the expanding step (temperature, tension, etc.), and may be, for example, 1 to 200 μm, 5 to 50 μm, or 10 to 20 μm. If the thickness of the pressure-sensitive adhesive layer 3 is 1 μm or more, the adhesiveness is unlikely to be insufficient, and if it is 200 μm or less, the calf width becomes wide when expanding (without relaxing the stress when pushing up the pin), and the pickup is not possible. It tends to be difficult to be sufficient.

The pressure-sensitive adhesive layer 3 is formed on the base material layer 1. As a method for forming the pressure-sensitive adhesive layer 3, a known method can be adopted. For example, a laminate of the base material layer 1 and the pressure-sensitive adhesive layer 3 may be formed by a two-layer extrusion method, or an active energy ray-curable pressure-sensitive adhesive varnish (varnish for forming a pressure-sensitive adhesive layer) may be prepared. This may be applied to the surface of the base material layer 1, or the pressure-sensitive adhesive layer 3 may be formed on the film that has been mold-released, and this may be transferred to the base material layer 1.

The active energy ray-curable pressure-sensitive adhesive varnish (varnish for forming a pressure-sensitive adhesive layer) is an organic solvent capable of dissolving a (meth) acrylic resin, a photopolymerization initiator, and a cross-linking agent, and is volatilized by heating. It may be there. Specific examples of the organic solvent include aromatic hydrocarbons such as toluene, xylene, mesityrene, cumene, and p-simene; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; methanol, ethanol, isopropanol, butanol, ethylene glycol, and propylene. Alcohols such as glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, etc. Estel: Carbonated esters such as ethylene carbonate and propylene carbonate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Polyhydric alcohol alkyl ethers such as dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Polyhydric alcohol alkyl ether acetates such as butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; N, N-dimethylformamide, N, N-dimethylacetamide, N Examples thereof include amides such as −methyl-2-pyrrolidone. These organic solvents may be used alone or in combination of two or more.

Among these, organic solvents are, for example, toluene, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether from the viewpoint of solubility and boiling point. , Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and at least one selected from the group consisting of N, N-dimethylacetamide. It may be there. The solid content concentration of the varnish is usually 10 to 60% by mass.

(Base layer)
The base material layer 1 is not particularly limited as long as a known polymer sheet or film can be used and the expanding step can be carried out under low temperature conditions. Specific examples of the base material layer 1 include polyolefins such as crystalline polypropylene, amorphous polypropylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, low-density linear polyethylene, polybutene, and polymethylpentene. , Ethylene-vinyl acetate copolymer, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester (random, alternating) copolymer, ethylene-butene copolymer, ethylene-hexene Copolymers, polyurethanes, polyethylene terephthalates, polyesters such as polyethylene naphthalate, polycarbonates, polyimides, polyether ether ketones, polyimides, polyetherimides, polyamides, total aromatic polyamides, polyphenylsulfides, aramids (paper), glass, Examples thereof include glass cloth, fluororesin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, silicone resin, a mixture of these mixed with a plasticizer, and a cured product crosslinked by electron beam irradiation.

The base material layer 1 has a surface containing at least one resin selected from the group consisting of polyethylene, polypropylene, polyethylene-polypropylene random copolymer, and polyethylene-polypropylene block copolymer as a main component, and the surface thereof. It may be in contact with the pressure-sensitive adhesive layer 3. These resins can be good base materials from the viewpoints of Young's modulus, stress relaxation property, characteristics such as melting point, price, and recycling of waste materials after use. The base material layer 1 may be a single layer, and may have a multilayer structure in which layers made of different materials are laminated, if necessary. From the viewpoint of controlling the adhesion to the pressure-sensitive adhesive layer 3, the surface of the base material layer 1 may be subjected to a surface roughness treatment such as a matte treatment or a corona treatment.

(Adhesive layer)
An adhesive composition constituting a known die bonding film can be applied to the adhesive layer 5. Specifically, the adhesive composition constituting the adhesive layer 5 may contain a reactive group-containing (meth) acrylic copolymer, a curing accelerator, and a filler. According to the adhesive layer 5 containing these components, the adhesiveness between chips / substrates and between chips / chips is excellent, electrode embedding property, wire embedding property, etc. can be imparted, and the die bonding process is performed at a low temperature. It tends to have characteristics such as being able to adhere and being able to obtain excellent curing in a short time, and having excellent reliability after being molded with a sealing agent.

The reactive group-containing (meth) acrylic copolymer may be, for example, an epoxy group-containing (meth) acrylic copolymer. The epoxy group-containing (meth) acrylic copolymer may be a copolymer obtained by using glycidyl (meth) acrylate as a raw material in an amount of 0.5 to 6% by mass with respect to the obtained copolymer. When the content of glycidyl (meth) acrylate is 0.5% by mass or more, high adhesive strength can be easily obtained, while when it is 6% by mass or less, gelation tends to be suppressed. The monomer constituting the remainder of the reactive group-containing (meth) acrylic copolymer is, for example, an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms such as methyl (meth) acrylate, styrene, acrylonitrile, or the like. It's okay. Among these, the monomer constituting the remainder of the reactive group-containing (meth) acrylic copolymer may be ethyl (meth) acrylate and / or butyl (meth) acrylate. The mixing ratio can be adjusted in consideration of the Tg of the reactive group-containing (meth) acrylic copolymer. When the Tg is −10 ° C. or higher, the tackiness of the adhesive layer 5 in the B stage state tends to be suppressed from becoming too large, and the handleability tends to be excellent. The glass transition point (Tg) of the epoxy group-containing (meth) acrylic copolymer may be, for example, 30 ° C. or lower. The polymerization method is not particularly limited, and examples thereof include pearl polymerization and solution polymerization. Examples of commercially available epoxy group-containing (meth) acrylic copolymers include HTR-860P-3 (trade name, manufactured by Nagase ChemteX Corporation).

The weight average molecular weight of the epoxy group-containing (meth) acrylic copolymer may be 100,000 or more, and may be 300,000 to 3,000,000 or 500,000 to 2,000,000 from the viewpoint of adhesiveness and heat resistance. When the weight average molecular weight is 3 million or less, it is possible to suppress a decrease in the filling property between the chip and the substrate supporting the chip. The weight average molecular weight is a polystyrene-equivalent value using a calibration curve made of standard polystyrene by gel permeation chromatography (GPC).

Examples of the curing accelerator include tertiary amines, imidazoles, quaternary ammonium salts and the like. Specific examples of the curing accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitate. One of these may be used alone, or two or more thereof may be used in combination.

The filler may be an inorganic filler. Specific examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, and boron nitride. Examples include crystalline silica and amorphous silica. One of these may be used alone, or two or more thereof may be used in combination.

The adhesive composition may further contain an epoxy resin and an epoxy resin curing agent. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. Bisphenol A novolak type epoxy resin, diglycidyl etherified product of biphenol, diglycidyl etherified product of naphthalenediol, diglycidyl etherified product of phenols, diglycidyl etherified product of alcohols, and alkyl substituents and halides thereof. , Bifunctional epoxy resin such as hydrogen additive, novolak type epoxy resin and the like. Further, other generally known epoxy resins such as a polyfunctional epoxy resin and a heterocycle-containing epoxy resin may be applied. These can be used alone or in combination of two or more. In addition, a component other than the epoxy resin may be contained as an impurity as long as the characteristics are not impaired.

Examples of the epoxy resin curing agent include a phenol resin obtained by reacting a phenol compound with a xylylene compound which is a divalent linking group in the presence of a non-catalyst or an acid catalyst. Examples of the phenolic compound used for producing the phenolic resin include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, on-propylphenol, and mn-propyl. Phenol, pn-propylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutyl Phenol, p-isobutylphenol, octylphenol, nonylphenol, 2,4-xylenol, 2,6-xylenol, 3,5-xylenol, 2,4,6-trimethylphenol, resorcin, catechol, hydroquinone, 4-methoxyphenol, o -Phenylphenol, m-phenylphenol, p-phenylphenol, p-cyclohexylphenol, o-allylphenol, p-allylphenol, o-benzylphenol, p-benzylphenol, o-chlorophenol, p-chlorophenol, o Examples thereof include −bromophenol, p-bromophenol, o-iodophenol, p-iodophenol, o-fluorophenol, m-fluorophenol, p-fluorophenol and the like. These phenol compounds may be used alone or in combination of two or more. As the xylylene compound which is a divalent linking group used in the production of a phenol resin, the following xylylene halides, xylylene diglycols and derivatives thereof can be used. That is, specific examples of the xylene compound include α, α'-dichloro-p-xylene, α, α'-dichloro-m-xylene, α, α'-dichloro-o-xylene, α, α'-dibromo-. p-xylene, α, α'-dibromo-m-xylene, α, α'-dibromo-o-xylene, α, α'-diiodo-p-xylene, α, α'-diiodo-m-xylene, α, α'-diiodo-o-xylene, α, α'-dihydroxy-p-xylene, α, α'-dihydroxy-m-xylene, α, α'-dihydroxy-o-xylene, α, α'-dimethoxy-p -Xylene, α, α'-dimethoxy-m-xylene, α, α'-dimethoxy-o-xylene, α, α'-diethoxy-p-xylene, α, α'-diethoxy-m-xylene, α, α '-Diethoxy-o-xylene, α, α'-di-n-propoxy-p-xylene, α, α'-di-n-propoxy-m-xylene, α, α'-di-n-propoxy-o -Xylene, α, α'-diisopropoxy-p-xylene, α, α'-diisopropoxy-m-xylene, α, α'-diisopropoxy-o-xylene, α, α'-di-n -Butoxy-p-xylene, α, α'-di-n-butoxy-m-xylene, α, α'-di-n-butoxy-o-xylene, α, α'-diisobutoxy-p-xylene, α, α'-diisobutoxy-m-xylene, α, α'-diisobutoxy-o-xylene, α, α'-di-tert-butoxy-p-xylene, α, α'-di-tert-butoxy-m-xylene, Examples thereof include α and α'-di-tert-butoxy-o-xylene. These may be used alone or in combination of two or more.

When reacting a phenol compound with a xylylene compound, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and polyphosphoric acid; organic carboxylic acids such as dimethylsulfate, diethylsulfate, p-toluenesulfonic acid, methanesulfonic acid, and ethanesulfonic acid. Acids; Super-strong acids such as trifluoromethanesulfonic acid; Strongly acidic ion exchange resins such as alcan sulfonic acid type ion exchange resin; Super strong acid ion exchange resins such as perfluoroalkane sulfonic acid type ion exchange resin (trade name) : Nafion, Nafion, manufactured by Du Pont, "Nafion" is a registered trademark); natural and synthetic zeolites; xylylene which is a substantially raw material at 50 to 250 ° C. using an acidic catalyst such as active white clay (acidic white clay). A phenol resin can be obtained by reacting until the compound disappears and the reaction composition becomes constant. The reaction time can be appropriately set depending on the raw material and the reaction temperature, for example, about 1 hour to 15 hours, and can be determined while tracking the reaction composition by GPC (gel permeation chromatography) or the like. ..

The thickness of the adhesive layer 5 may be, for example, 1 to 300 μm, 5 to 150 μm, or 10 to 100 μm. When the thickness of the adhesive layer 5 is 1 μm or more, the adhesiveness tends to be more excellent, while when the thickness of the adhesive layer 5 is 300 μm or less, the splitting property and the pick-up property at the time of expanding tend to be more excellent.

<Manufacturing method of dicing / die bonding integrated film>
The method for producing the film 10 is to: on the surface of the base material layer 1 a pressure-sensitive adhesive layer made of an active energy ray-curable pressure-sensitive adhesive whose adhesive strength is reduced by irradiation with active energy rays, and on the surface of the pressure-sensitive adhesive layer. A step of producing a laminated body including the adhesive layer 5 formed in the above, and a step of irradiating a region to be a first region 3a of the pressure-sensitive adhesive layer contained in the laminated body with active energy rays are provided in this order. .. The irradiation amount of the active energy ray to the region to be the first region 3a may be, for example, 10 to 1000 mJ / cm ² , 100 to 700 mJ / cm ² , or 200 to 500 mJ / cm ² . In the manufacturing method, a laminate of the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer 5 is first produced, and then a specific region of the pressure-sensitive adhesive layer is irradiated with active energy rays.

<Semiconductor device and its manufacturing method>
FIG. 4 is a cross-sectional view schematically showing the semiconductor device according to the present embodiment. The semiconductor device 100 shown in this figure includes a substrate 70, four chips S1, S2, S3, S4 laminated on the surface of the substrate 70, electrodes (not shown) on the surface of the substrate 70, and four chips. A wire W1, W2, W3, W4 for electrically connecting S1, S2, S3, and S4, and a sealing layer 50 for sealing these are provided.

The substrate 70 is, for example, an organic substrate and may be a metal substrate such as a lead frame. The thickness of the substrate 70 may be, for example, 70 to 140 μm or 80 to 100 μm from the viewpoint of suppressing the warp of the semiconductor device 100.

The four chips S1, S2, S3, and S4 are laminated via the cured product 5C of the adhesive piece 5P. The shapes of the chips S1, S2, S3, and S4 in a plan view are, for example, square or rectangular. The area of the chips S1, S2, S3, S4 is 0.1 to 9 mm ² , and may be ^{0.1 to 4 mm 2} or 0.1 to 2 mm 2. The length of one side of the chips S1, S2, S3, and S4 may be, for example, 0.1 to 3 mm, 0.1 to 2 mm, or 0.1 to 1 mm. The thickness of the chips S1, S2, S3, S4 may be, for example, 10 to 170 μm or 25 to 100 μm. The length of one side of the four chips S1, S2, S3, and S4 may be the same or different from each other, and the thickness is also the same.

The method for manufacturing the semiconductor device 100 includes the step of preparing the film 10 described above, attaching the wafer W to the adhesive layer 5 of the film 10, and dicing ring DR on the second surface F2 of the adhesive layer 3. The adhesive layer 3 includes a step of attaching the wafer W, a step of separating the wafer W into a plurality of chips S (dicing step), and a DAF8 (a laminate of the chip S1 and the adhesive piece 5P, see FIG. 5D). A step of picking up from the first region 3a of the above and a step of mounting the chip S1 on the substrate 70 via the adhesive piece 5P are provided.

An example of a method for producing DAF8 will be described with reference to FIGS. 5 (a), 5 (b), 5 (c), and 5 (d). First, the above-mentioned film 10 is prepared. As shown in FIGS. 5A and 5B, the film 10 is attached so that the adhesive layer 5 is in contact with one surface of the wafer W. Further, the dicing ring DR is attached to the second surface F2 of the pressure-sensitive adhesive layer 3.

The wafer W, the adhesive layer 5, and the adhesive layer 3 are diced. As a result, as shown in FIG. 5C, the wafer W is fragmented into chips S. The adhesive layer 5 is also individualized to become an adhesive piece 5P. Examples of the dicing method include a method using a dicing blade or a laser. The wafer W may be thinned by grinding the wafer W prior to dicing the wafer W.

After dicing, the adhesive layer 3 is separated from each other by expanding the base material layer 1 under normal temperature or cooling conditions as shown in FIG. 5D without irradiating the pressure-sensitive adhesive layer 3 with active energy rays. The adhesive piece 5P is peeled from the adhesive layer 3 by pushing it up with the pin 42, and the DAF 8 is sucked and picked up by the suction collet 44.

The manufacturing method of the semiconductor device 100 will be specifically described with reference to FIGS. 6, 7, and 8. First, as shown in FIG. 6, the first-stage chip S1 (chip S) is crimped to a predetermined position on the substrate 70 via the adhesive piece 5P. Next, the adhesive piece 5P is cured by heating. As a result, the adhesive piece 5P is cured to become a cured product 5C. The curing treatment of the adhesive piece 5P may be carried out in a pressurized atmosphere from the viewpoint of reducing voids.

The second-stage chip S2 is mounted on the surface of the chip S1 in the same manner as the mounting of the chip S1 on the substrate 70. Further, the structure 60 shown in FIG. 7 is manufactured by mounting the third-stage and fourth-stage chips S3 and S4. After the chips S1, S2, S3, S4 and the substrate 70 are electrically connected by wires W1, W2, W3, W4 (see FIG. 8), the semiconductor element and the wire are sealed by the sealing layer 50. The semiconductor device 100 shown in 4 is completed.

Although the embodiments of the present disclosure have been described in detail above, the present invention is not limited to the above embodiments. For example, in the above embodiment, the film 10 including the base material layer 1, the pressure-sensitive adhesive layer 3, and the adhesive layer 5 in this order has been exemplified, but the film 10 may not include the adhesive layer 5. .. Further, the film 10 may further include a cover film (not shown) that covers the adhesive layer 5.

Hereinafter, the present disclosure will be described in more detail based on Examples, but the present invention is not limited to these Examples. Unless otherwise specified, all chemicals used were reagents.

<Manufacturing example 1>
[Synthesis of acrylic resin (A-1)]
The following components were placed in a 2000 mL flask equipped with a three-one motor, a stirring blade, and a nitrogen introduction tube.
-Ethyl acetate (solvent): 635 parts by mass-2-Ethylhexyl acrylate: 395 parts by mass-2-Hydroxyethyl acrylate: 100 parts by mass-Methacrylic acid: 5 parts by mass-Azobisisobutyronitrile: 0.08 parts by mass

After stirring the contents until they were sufficiently uniform, bubbling was carried out at a flow rate of 500 mL / min for 60 minutes to degas the dissolved oxygen in the system. The temperature was raised to 78 ° C. over 1 hour, and after the temperature was raised, polymerization was carried out for 6 hours. Next, the reaction solution was transferred to a pressure kettle having a capacity of 2000 mL equipped with a three-one motor, a stirring blade, and a nitrogen introduction tube, heated at 120 ° C. and 0.28 MPa for 4.5 hours, and then at room temperature (25 ° C.). , And so on).

Next, 490 parts by mass of ethyl acetate was added and stirred to dilute the contents. To this, 0.10 parts by mass of dioctyltin dilaurate was added as a urethanization catalyst, and then 48.6 parts by mass of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karens MOI (trade name)) was added to 70 parts. After reacting at ° C. for 6 hours, the mixture was cooled to room temperature. Next, ethyl acetate is further added to adjust the non-volatile content in the acrylic resin solution to 35% by mass, and the acrylic resin (A-1) having a chain-growth-polymerizable functional group of Production Example 1 is contained. A solution was obtained.

The solution containing the acrylic resin (A-1) obtained as described above was vacuum dried at 60 ° C. overnight. The solid content thus obtained was elementally analyzed by a fully automatic elemental analyzer (manufactured by Elemental Co., Ltd., trade name: varioEL), and the content of the functional group derived from the introduced 2-methacryloyloxyethyl isocyanate was nitrogen-containing. When calculated from the amount, it was 0.50 mmol / g.

In addition, the polystyrene-equivalent weight average molecular weight of the acrylic resin (A-1) was determined using the following apparatus. That is, SD-8022 / DP-8020 / RI-8020 manufactured by Tosoh Corporation was used, Gelpack GL-A150-S / GL-A160-S manufactured by Hitachi Kasei Co., Ltd. was used for the column, and tetrahydrofuran was used as the eluent. GPC measurement was performed. As a result, the polystyrene-equivalent weight average molecular weight was 800,000. The hydroxyl value and acid value measured according to the method described in JIS K0070 were 56.1 mgKOH / g and 6.5 mgKOH / g. These results are summarized in Table 1.

<Manufacturing example 2>
[Synthesis of acrylic resin (A-2)]
The acrylic resin (A-2) of Production Example 2 was prepared in the same manner as in Production Example 1 except that the raw material monomer composition shown in Production Example 1 in Table 1 was changed to the raw material monomer composition shown in Production Example 2 in Table 1. A solution containing the above was obtained. Table 1 shows the measurement results of the properties of the acrylic resin (A-2) of Production Example 2.

<Manufacturing example 3>
[Synthesis of acrylic resin (A-3)]
The acrylic resin (A-3) of Production Example 3 was prepared in the same manner as in Production Example 1 except that the raw material monomer composition shown in Production Example 1 in Table 1 was changed to the raw material monomer composition shown in Production Example 3 in Table 1. A solution containing the above was obtained. Table 1 shows the measurement results of the properties of the acrylic resin (A-3) of Production Example 3.

<Example 1>
[Preparation of dicing film (adhesive layer)]
By mixing the following components, an active energy ray-curable pressure-sensitive adhesive varnish (varnish for forming a pressure-sensitive adhesive layer) was prepared (see Table 2). The amount of ethyl acetate (solvent) was adjusted so that the total solid content of the varnish was 25% by mass.
-Solution containing the acrylic resin (A-1) of Production Example 1: 100 parts by mass (solid content)
-Photopolymerization initiator (B-1) (1-hydroxycyclohexyl-phenyl-ketone (manufactured by Ciba Speciality Chemicals Co., Ltd., Irgacure 184, "Irgacure" is a registered trademark): 1.0 part by mass-crosslinking agent (C-1) ) (Polyfunctional isocyanate (reactant of tolylene diisocyanate and trimethylolpropane), manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L, solid content: 75%): 8.0 parts by mass (solid content)
・ Ethyl acetate (solvent)

A polyethylene terephthalate film (width 450 mm, length 500 mm, thickness 38 μm) having a mold release treatment on one surface was prepared. A varnish of an active energy ray-curable pressure-sensitive adhesive was applied to the surface subjected to the mold release treatment using an applicator, and then dried at 80 ° C. for 5 minutes. As a result, a laminate (dicing film) composed of a polyethylene terephthalate film and a pressure-sensitive adhesive layer having a thickness of 30 μm formed on the polyethylene terephthalate film was obtained.

A polyolefin film (width 450 mm, length 500 mm, thickness 80 μm) having a corona treatment on one surface was prepared. The surface treated with corona and the pressure-sensitive adhesive layer of the laminated body were bonded together at room temperature. Then, the pressure-sensitive adhesive layer was transferred to the polyolefin film (cover film) by pressing with a rubber roll. Then, it was left at room temperature for 3 days to obtain a dicing film with a cover film.

[Preparation of die bonding film (adhesive layer)]
A varnish for forming an adhesive layer was prepared by mixing the following components. First, cyclohexanone (solvent) was added to the mixture containing the following components, and the mixture was stirred and mixed, and then kneaded for 90 minutes using a bead mill.
-Epoxy resin (YDCN-700-10 (trade name), manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., cresol novolac type epoxy resin, epoxy equivalent: 210, molecular weight: 1200, softening point: 80 ° C.): 14 parts by mass-phenol resin ( Millex XLC-LL (trade name), manufactured by Mitsui Chemicals, Inc., phenol resin, hydroxyl group equivalent: 175, water absorption: 1.8%, heating weight reduction rate at 350 ° C: 4%): 23 parts by mass, silane coupling Agent (NUC A-189 (trade name) manufactured by NUC Co., Ltd., γ-mercaptopropyltrimethoxysilane): 0.2 parts by mass · silane coupling agent (NUCA-1160 (trade name) manufactured by Nippon Unicar Co., Ltd., γ -Ureidopropyltriethoxysilane): 0.1 parts by mass · Filler (SC2050-HLG (trade name), manufactured by Admatex Co., Ltd., silica, average particle size 0.500 μm): 32 parts by mass

After further adding the following components to the mixture obtained as described above, a varnish for forming an adhesive layer (at least with a reactive group-containing (meth) acrylic copolymer) is subjected to the steps of stirring and mixing and vacuum degassing. , A varnish of an adhesive composition containing a curing accelerator and a filler) was obtained.
-Epoxide group-containing acrylic copolymer (HTR-860P-3 (trade name), manufactured by Nagase ChemteX Corporation, weight average molecular weight 800,000): 16 parts by mass-curing accelerator (Curesol 2PZ-CN (trade name), 1-Cyanoethyl-2-phenylimidazole manufactured by Shikoku Kasei Kogyo Co., Ltd., "Curesol" is a registered trademark) 0.1 parts by mass

A polyethylene terephthalate film (thickness 35 μm) having a mold release treatment on one surface was prepared. A varnish for forming an adhesive layer was applied to the surface subjected to the mold release treatment using an applicator, and then heat-dried at 140 ° C. for 5 minutes. As a result, a laminate (die bonding film) composed of a polyethylene terephthalate film (carrier film) and an adhesive layer (B stage state) having a thickness of 25 μm formed on the polyethylene terephthalate film (carrier film) was obtained.

[Preparation of dicing / die bonding integrated film]
A die bonding film composed of an adhesive layer and a carrier film was cut into a circle having a diameter of 335 mm together with the carrier film. A dicing film from which the polyethylene terephthalate film was peeled off was attached to the cut die bonding film at room temperature, and then left at room temperature for 1 day. Then, the dicing film was cut into a circle having a diameter of 370 mm to obtain a laminated body. The region (first region of the pressure-sensitive adhesive layer) corresponding to the bonding position of the wafer in the adhesive layer of the laminated body thus obtained was irradiated with ultraviolet rays as follows. That is, a pulsed xenon lamp was used to partially irradiate ultraviolet rays at an irradiation amount of ^{70 W and 300 mJ / cm 2.} The irradiation of ultraviolet rays was performed on a portion having an inner diameter of 318 mm from the center of the film using a blackout curtain. In this way, a plurality of dicing / die bonding integrated films of Example 1 were obtained for use in various evaluation tests described later.

<Example 2>
A plurality of dicing / die bonding integrated films of Example 2 were obtained in the same manner as in Example 1 except that the irradiation amount of ultraviolet rays ^{was changed from 300 mJ / cm 2} to 200 mJ / cm ^2.

<Example 3>
A plurality of dicing / die bonding integrated films of Example 3 were obtained in the same manner as in Example 1 except that the irradiation amount of ultraviolet rays ^{was changed from 300 mJ / cm 2} to 500 mJ / cm ^2.

<Example 4>
The photopolymerization initiator (B-1) used in producing the dicing film was used as the photopolymerization initiator (B-2) (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl)]. -Propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, manufactured by Tivas Specialty Chemicals Co., Ltd., Irgacure 127, "Irgacure" is a registered trademark)), except that it is the same as in Example 1. Therefore, a plurality of dicing / die bonding integrated films of Example 4 were obtained.

<Example 5>
A plurality of dicing dies of Example 5 are carried out in the same manner as in Example 3 except that the acrylic resin (A-1) used for producing the dicing film is changed to the acrylic resin (A-2). A bonding integrated film was obtained.

<Comparative example 1>
A plurality of dicing dies of Comparative Example 1 were obtained in the same manner as in Example 1 except that the acrylic resin (A-1) used for producing the dicing film was changed to the acrylic resin (A-3). A bonding integrated film was obtained.

[Evaluation test]
(1) Measurement of Adhesive Strength (30 ° Peel Strength) of Adhesive Layer to Adhesive Layer Adhesive Strength (F1) of the first region of the adhesive layer to the adhesive layer and the second adhesive layer to the adhesive layer The adhesive strength (F2) of the region was evaluated by measuring the 30 ° peel strength. F1 corresponds to the adhesive force of the first region of the pressure-sensitive adhesive layer after irradiation of the adhesive layer with ultraviolet rays, and F2 corresponds to the first region of the pressure-sensitive adhesive layer before irradiation of the adhesive layer with ultraviolet rays. Corresponds to the adhesive strength of the area. Therefore, F1 uses the dicing / diebonding integrated film after irradiation with ultraviolet rays in [Preparation of dicing / diebonding integrated film], and F2 uses the laminate before irradiation with ultraviolet rays to obtain adhesive strength (adhesive strength). 30 ° peel strength) was measured. The measurement sample was obtained by preparing a dicing / die bonding integrated film and a laminate, and cutting them into a width of 25 mm and a length of 100 mm, respectively. Using a tensile tester (manufactured by Shimadzu Corporation, Autograph "AGS-1000"), the peel strength and adhesive in the first region of the adhesive layer after irradiation of the adhesive layer with ultraviolet rays from each measurement sample. The peel strength of the region serving as the first region of the pressure-sensitive adhesive layer before irradiation of the layer with ultraviolet rays (the peel strength of the second region of the pressure-sensitive adhesive layer with respect to the adhesive layer) was measured. The measurement conditions were a peeling angle of 30 ° and a peeling speed of 60 mm / min. The sample was stored and the peel strength was measured in an environment of a temperature of 23 ° C. and a relative humidity of 40%. The results are shown in Table 2.

(2) Measurement of Adhesive Strength (90 ° Peel Strength) of Adhesive Layer to Stainless Substrate The adhesive strength of the second region of the adhesive layer to the stainless substrate was evaluated by measuring 90 ° peel strength. The adhesive strength corresponds to the adhesive strength of the pressure-sensitive adhesive layer before irradiation with ultraviolet rays on the stainless steel substrate. Therefore, the adhesive strength (90 ° peel strength) was measured using the laminated body before irradiation with ultraviolet rays in [Preparation of dicing / die bonding integrated film]. The measurement sample was obtained by preparing a laminate, cutting it into a width of 25 mm and a length of 100 mm, and attaching the surface on the adhesive layer side to a stainless steel substrate (SUS430BA). The peel strength of the pressure-sensitive adhesive layer on the stainless steel substrate was measured from the measurement sample using a tensile tester (manufactured by Shimadzu Corporation, Autograph "AGS-1000"). The measurement conditions were a peeling angle of 90 ° and a peeling speed of 50 mm / min. The results are shown in Table 2.

(3) Measurement of Curing Shrinkage Rate of Adhesive Layer Two polyethylene terephthalate films (width 450 mm, length 500 mm, thickness 38 μm) having a mold release treatment on one surface were prepared. A varnish of an active energy ray-curable adhesive was applied to the release-treated surface of one polyethylene terephthalate film using an applicator, and then dried at 80 ° C. for 5 minutes to form an adhesive layer. .. Next, the surface of the other polyethylene terephthalate film subjected to the mold release treatment and the pressure-sensitive adhesive layer are bonded together at room temperature and pressed with a rubber roll to obtain the polyethylene terephthalate film and a pressure-sensitive adhesive layer having a thickness of 30 μm. And a laminate made of a polyethylene terephthalate film was obtained. A plurality of such laminates were produced. Next, the polyethylene terephthalate film of the laminated body is peeled off on one side, the adhesive layers are laminated so that voids do not enter, and this is adhered using another laminated body until the thickness of the adhesive layer becomes about 1 mm. By repeating laminating the agent layers, a laminate composed of two polyethylene terephthalate films and an adhesive layer having a thickness of about 1 mm sandwiched between them was obtained.

The obtained laminate was punched to a diameter of 10 mmφ, the polyethylene terephthalate film was peeled off on both sides, and the laminate was placed on a slide glass so as not to contain voids. Next, a sample was obtained by punching an aluminum foil having a black side to 10 mmφ in the same manner and arranging it on the upper surface of the adhesive layer on the opposite side to the slide glass. The obtained sample is irradiated with ultraviolet rays under the same conditions as in [Preparation of dicing / die bonding integrated film], and the ultraviolet rays are exposed using a resin curing shrinkage measuring device (Custron, manufactured by Acroedge Co., Ltd.). The curing shrinkage was measured from the difference in thickness excluding the slide glass and aluminum foil before and after irradiation. The results are shown in Table 2.

(4) Measurement of chip edge peeling strength The edge peeling strength is measured through the following steps. 9 (a), 9 (b), and 9 (c) are cross-sectional views schematically showing a step of measuring the edge peeling strength.
A step of attaching a silicon wafer Ws having a thickness of 50 μm to the adhesive layer 5 and attaching a dicing ring DR to the second surface F2 of the adhesive layer 3 (see FIG. 9A).
-A step of individualizing the silicon wafer Ws and the adhesive layer 5 into a plurality of chips Ta with adhesive pieces (a laminate of chips Ts and adhesive pieces 5p) (see FIG. 9B).
-At a temperature of 23 ° C., the central portion of the adhesive pieced chip Ta is pushed in from the base material layer 1 side at a speed of 60 mm / min (see FIG. 9C), and the edge of the adhesive pieced chip Ta is peeled off from the adhesive layer 3. The process of measuring the edge peeling strength at the time

First, a dicing / dicing-bonding integrated film was attached to a silicon wafer (diameter: 12 inches, thickness: 50 μm) and a dicing ring under the following conditions (see FIG. 9A). The elongation of the dicing / dicing-bonding integrated film in the MD direction after the silicon wafer and the dicing ring were attached was about 1.0 to 1.3%.

<Attachment conditions>
-Attachment device: DFM2800 (manufactured by Disco Corporation)
-Attachment temperature: 70 ° C
-Attachment speed: 10 mm / s
・ Sticking tension level: Level 6

Next, the silicon wafer with the dicing / die bonding integrated film was separated into a plurality of chips with adhesive pieces (size 2 mm × 2 mm) by blade dicing (see FIG. 9 (b)).

<Dicing conditions>
・ Dicer: DFD6361 (manufactured by Disco Corporation)
-Blade: ZH05-SD4000-N1-70-BB (manufactured by Disco Corporation)
・ Blade rotation speed: 40,000 rpm
・ Dicing speed: 30 mm / sec ・ Blade height: 90 μm
-Cut depth from the surface of the adhesive layer to the base material layer: 20 μm
・ Amount of water during dicing Blade cooler: 1.5L / min Shower: 1.0L / min,
Spray: 1.0 L / min

One day after dicing, the chip with the adhesive piece was pushed in from the base material layer side with the jig P under the following measurement conditions, and the edge peeling strength of the tip with the adhesive piece was measured (see FIG. 9C). FIG. 10 is a graph showing an example of the relationship between the displacement (mm) due to pushing and the pushing force (N). When the edge of the chip is peeled off, as shown in FIG. 10, the pushing force temporarily decreases, and a change point occurs in the graph. The value of the pushing force at this change point is defined as the edge peeling strength. Before the measurement, the surface of the base material layer corresponding to the central portion of the chip was marked with an oil-based pen. FIG. 11 is a plan view schematically showing a state in which a mark is added at a position corresponding to the central portion of the chip to be measured. The mark M at the center of the chip was identified by measuring with a ruler. The measurement was performed at N = 10. After measuring one chip, the next measurement was performed with an interval of three chips (see FIG. 11). The results are shown in Table 2.

<Measurement conditions>
・ Measuring device: Small desktop tester EZ-SX (manufactured by Shimadzu Corporation)
・ Load cell: 50N
・ Pushing jig: Attachment attached to ZTS series (Shape: Conical, manufactured by Imada Co., Ltd.)
・ Pushing speed: 60 mm / min ・ Temperature: 23 ° C
・ Humidity: 45 ± 10%

(5) Evaluation of Pickupability After measuring the edge peeling strength described above, 100 chips with adhesive pieces were picked up under the following conditions.

<Pickup conditions>
・ Die bonder device: DB800-HSD (manufactured by Hitachi High-Technologies Corporation)
-Push pin: EJECTOR NEEDLE SEN2-83-05 (diameter: 0.7 mm, tip shape: hemisphere with radius 350 μm, manufactured by Micromechanics)
・ Push-up height: 200 μm
・ Push-up speed: 1 mm / sec,
One push-up pin was arranged at the center of the chip. The pickup success rate was 100% as "A", 70% or more and less than 100% as "B", and less than 70% as "C". The results are shown in Table 2.

As shown in Table 2, the dicing / die bonding integrated film of Examples 1 to 5 had better pick-up performance than the dicing / die bonding integrated film of Comparative Example 1. Specifically, in Comparative Example 1, since the difference in (F1-F2) is larger than in Examples 1 to 5, the curing shrinkage rate and the edge peeling strength are also higher than in Examples 1 to 5, and the pick-up property is sufficient. It wasn't. From the above results, the dicing / die bonding integrated film of the present disclosure can be applied to a manufacturing process of a semiconductor device including a step of fragmenting ^{a wafer into a plurality of small chips (area 0.1 to 9 mm 2).} It was confirmed that the adhesive layer had an excellent pick-up property.

1 ... base material layer, 3 ... adhesive layer, 3a ... first region, 3b ... second region, 5 ... adhesive layer, 5P, 5p ... adhesive piece, 5C ... cured product, 8 ... DAF, 10 ... Dicing / die bonding integrated film (film), 42 ... Pin, 44 ... Suction collet, 50 ... Sealing layer, 60 ... Structure, 70 ... Substrate, 80 ... Support plate, 100 ... Semiconductor device, DR ... Dicing ring , F1 ... 1st surface, F2 ... 2nd surface, M ... mark, P ... push-in jig, Rw ... area, S1, S2, S3, S4, S, Ts ... chip, Ta ... adhesive pieced chip, W ... Wafer, Ws ... Silicon wafer, W1, W2, W3, W4 ... Wire.

Claims (12)

Base layer and
A pressure-sensitive adhesive layer made of an active energy ray-curable pressure-sensitive adhesive, which has a first surface facing the base material layer and a second surface opposite to the first surface.
An adhesive layer provided so as to cover the central portion of the second surface, and
With
The pressure-sensitive adhesive layer has a first region including at least a region corresponding to a wafer attachment position in the adhesive layer, and a second region located so as to surround the first region.
The first region is a region in which the adhesive strength is reduced as compared with the second region due to irradiation with active energy rays.
The adhesive strength of the first region of the adhesive layer to the adhesive layer, which is measured at a temperature of 23 ° C. under the conditions of a peeling angle of 30 ° and a peeling speed of 60 mm / min, is F1 (N / 25 mm) and a temperature of 23 ° C. When the adhesive force of the second region of the adhesive layer with respect to the adhesive layer measured under the conditions of a peeling angle of 30 ° and a peeling speed of 60 mm / min is F2 (N / 25 mm), F2 and F1 The difference (F2-F1) from is 6.5 to 9.0 N / 25 mm.
It is applied to the manufacturing process of semiconductor devices including the step of fragmenting a wafer into a plurality of chips having an area of 0.1 to 9 mm ^2.
Dicing / die bonding integrated film. The difference (F2-F1) between F2 and F1 is 7.0 to 9.0 N / 25 mm.
The dicing / die bonding integrated film according to claim 1. The F1 is 1.1 to 4.5 N / 25 mm.
The dicing / die bonding integrated film according to claim 1 or 2. The F1 is 1.1 to 3.0 N / 25 mm.
The dicing / die bonding integrated film according to any one of claims 1 to 3. The adhesive strength of the second region of the pressure-sensitive adhesive layer to the stainless steel substrate, measured at a temperature of 23 ° C. under the conditions of a peeling angle of 90 ° and a peeling speed of 50 mm / min, is 0.2 N / 25 mm or more.
The dicing / die bonding integrated film according to any one of claims 1 to 4. The active energy ray-curable pressure-sensitive adhesive contains a (meth) acrylic resin having a functional group capable of chain polymerization.
The functional group is at least one selected from an acryloyl group and a methacryloyl group.
The content of the functional group in the (meth) acrylic resin is 0.1 to 1.2 mmol / g.
The dicing / die bonding integrated film according to any one of claims 1 to 5. The active energy ray-curable pressure-sensitive adhesive further contains a cross-linking agent.
The content of the cross-linking agent with respect to the total mass of the active energy ray-curable pressure-sensitive adhesive is 0.1 to 15% by mass.
The dicing / die bonding integrated film according to claim 6. The cross-linking agent is a reaction product of a polyfunctional isocyanate having two or more isocyanate groups in one molecule and a polyhydric alcohol having three or more hydroxy groups in one molecule.
The dicing / die bonding integrated film according to claim 7. The irradiation amount of the active energy ray is 10 to 1000 mJ / cm ² .
The dicing / die bonding integrated film according to any one of claims 1 to 8. The adhesive layer comprises an adhesive composition containing a reactive group-containing (meth) acrylic copolymer, a curing accelerator, and a filler.
The dicing / die bonding integrated film according to any one of claims 1 to 9. The method for producing a dicing / die bonding integrated film according to any one of claims 1 to 10.
A step of producing a laminate including an adhesive layer made of an active energy ray-curable pressure-sensitive adhesive and the adhesive layer formed on the surface of the pressure-sensitive adhesive layer on the surface of the base material layer.
A step of irradiating a region to be the first region of the pressure-sensitive adhesive layer contained in the laminate with active energy rays.
In this order,
A method for manufacturing a dicing / die bonding integrated film. The step of preparing the dicing / die bonding integrated film according to any one of claims 1 to 10.
A step of attaching a wafer to the adhesive layer of the dicing / die bonding integrated film and attaching a dicing ring to the second surface of the adhesive layer.
The process of individualizing the wafer into a plurality of chips and
A step of picking up the chip from the adhesive layer together with an adhesive piece obtained by separating the adhesive layer into individual pieces.
The step of mounting the chip on a substrate or another chip via the adhesive piece, and
To prepare
Manufacturing method of semiconductor devices.

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