KR20220100867A - Dicing and die-bonding integrated film, manufacturing method thereof, and semiconductor device manufacturing method - Google Patents

Abstract

Disclosed is a dicing die-bonding integrated film. The dicing and die-bonding integrated film includes a base layer, an adhesive layer having a first face facing the base layer and a second face on the opposite side, and an adhesive layer provided to cover the central portion of the second face. . The adhesive layer has a 1st area|region including the area|region corresponding to the affixing position of the wafer in an adhesive bond layer, and a 2nd area|region located so that it may surround it, The 1st area|region has adhesive force lowered compared with a 2nd area|region. It is an area in a state of being The pressure-sensitive adhesive layer WHEREIN: The difference between the adhesive force of the 1st area|region of the adhesive layer with respect to an adhesive bond layer, and the adhesive force of the 2nd area|region of the adhesive layer with respect to an adhesive bond layer, measured under predetermined conditions, is 6.5-9.0N/25mm.

Description

Dicing and die-bonding integrated film, manufacturing method thereof, and semiconductor device manufacturing method

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

A semiconductor device is manufactured through the following process. First, a dicing process is performed in the state which affixed the adhesive film for dicing on the wafer. After that, an expand process, a pickup process, a mounting process, a die bonding process, and the like are performed.

In the manufacturing process of a semiconductor device, the 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 bond layer were laminated|stacked in this order, and is used as follows, for example. First, the wafer is diced in the state which affixed the surface on the side of an adhesive bond layer with respect to a wafer, and fixed the wafer with a dicing ring. As a result, the wafer is divided into a plurality of chips. Then, after weakening the adhesive force of the adhesive layer with respect to an adhesive bond layer by irradiating an active energy ray with respect to an adhesive layer, a chip is picked up from an adhesive layer together with the adhesive bond piece from which an adhesive bond layer is divided into pieces. Thereafter, a semiconductor device is manufactured through a step of mounting the chip on a substrate or the like via an adhesive piece. In addition, the laminated body which consists of a chip|tip obtained through a dicing process, and the adhesive agent piece attached to it is called DAF (Die Attach Film).

As described above, the pressure-sensitive adhesive layer (dicing film) whose adhesive strength is weakened by irradiation with an active energy ray is called an active energy ray curing type. On the other hand, in the manufacturing process of a semiconductor device, an active energy ray is not irradiated, but the adhesive layer of the state in which adhesive force is fixed is called a pressure-sensitive type. A dicing and die-bonding integrated film having a pressure-sensitive adhesive layer does not require a step of irradiating an active energy ray for a user (mainly a semiconductor device maker), and is advantageous in that no equipment is required for this purpose. there is In patent document 1, it can be said that an adhesive layer contains the component hardened|cured by an active energy ray, and it can be said that it is an active energy ray hardening type. On the other hand, since the active energy ray is previously irradiated only to a predetermined portion of the pressure-sensitive adhesive layer, and the user does not need to irradiate the active energy ray in the semiconductor device manufacturing process, the dicing die-bonding integrated type, which can also be referred to as a pressure-sensitive adhesive layer. A film is disclosed.

Patent Document 1: Japanese Patent Publication No. 4443962

Generally, the adhesive layer of a dicing die-bonding integrated film is calculated|required that the adhesive force between an adhesive layer and an adhesive bond layer should be low. When the adhesive force is excessively high, in the chip pickup process, there is a possibility that a pickup error may occur and the yield may decrease. However, the present inventors found that when the chip to be produced by dicing becomes small (for example, 0.1 to 9 mm ² in area in a planar view), the pickup property of the chip is that of the pressure-sensitive adhesive layer and the adhesive layer. It was found that the peeling of the edge of the chip from the pressure-sensitive adhesive layer (hereinafter referred to as "edge peeling") was the dominant factor in the pick-up property, not necessarily dominant to the adhesive force between them. That is, the pick-up property of the small chip is mainly governed by the edge peel strength of the chip with the adhesive piece. guessed

As an influence factor of edge peeling strength, cure shrinkage of an adhesive layer is mentioned, for example. Usually, after a dicing process, in a dicing line, an adhesive bond layer, an adhesive layer, a wafer, etc. mix and generate|occur|produce a burr (cutting material) generate|occur|produces. When an adhesive layer is an active energy ray hardening type, by irradiation of an active energy ray, an adhesive layer may harden|cure together with a burr (cutting material), and there exists a possibility that edge peeling strength may increase significantly. If the pressure-sensitive adhesive layer is cured in advance before the dicing step, since there is no need to perform the step of irradiating active energy rays, there is no such effect, but the anchor effect at the adhesive layer interface due to curing shrinkage of the pressure-sensitive adhesive layer There exists a possibility that edge peeling strength may increase by this. As a result of the present inventors earnestly examining cure shrinkage of an adhesive layer, the magnitude|size of cure shrinkage has the tendency to become high, so that the difference of the adhesive force of the adhesive layer before and behind irradiation of the active energy ray with respect to an adhesive bond layer is large. Therefore, the present inventors are the difference between the adhesive force of the adhesive layer before irradiation with an active energy ray and the adhesive force of the adhesive layer after irradiation with an active energy ray (in other words, the adhesive force of the adhesive layer of the non-irradiated portion of the active energy ray and the adhesive of the irradiated portion of the active energy ray By adjusting the adhesive strength of the layers), the edge peeling strength could be reduced, and thus, the development of a dicing and die-bonding integrated film having excellent pickup properties was developed.

The present disclosure is applicable to a manufacturing process of a semiconductor device including a step of segmenting a wafer into a plurality of small chips (area 0.1 to 9 mm ² ), and dicing die bonding provided with an adhesive layer having excellent pickup properties Its main object is to provide an integral film and a method for manufacturing the same.

One aspect of the present disclosure relates to a dicing die-bonding integrated film. This film has a base layer, a pressure-sensitive adhesive layer made of an active energy ray-curable pressure-sensitive adhesive having a first face facing the base layer and a second face opposite to the first face, and the second face is provided to cover the central portion An adhesive layer is provided. The adhesive layer has a 1st area|region which contains at least the area|region corresponding to the affixing position of the wafer in an adhesive bond layer, and a 2nd area|region located so that the 1st area|region may be enclosed, and a 1st area|region is irradiated with an active energy ray. Thus, compared to the second region, the region is in a state in which the adhesive force is lowered. In the pressure-sensitive adhesive layer, the adhesive force of the first region of the pressure-sensitive adhesive layer to the adhesive layer, measured under the conditions of a peeling angle of 30° and a peeling rate of 60 mm/min at a temperature of 23° C., is f1 (N/25 mm), at a temperature of 23° C. The difference between f2 and f1 (f2-f1) when the adhesive force of the second region of the pressure-sensitive adhesive layer to the adhesive layer measured under the conditions of a peeling angle of 30° and a peeling rate of 60 mm/min is f2 (N/25 mm) Silver, 6.5~9.0N/25mm. This film is applied to a manufacturing process of a semiconductor device including a step of dividing 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, in that it is possible to reduce the edge peel strength by suppressing cure shrinkage of the pressure-sensitive adhesive layer, the wafer is divided into a plurality of small chips (area 0.1 to 9 mm ² ). It is applicable to the manufacturing process of the semiconductor device which says, and the outstanding pick-up property from an adhesive layer can be achieved.

The difference (f2-f1) between f2 and f1 may be 7.0 to 9.0 N/25 mm.

f1 (adhesive force of the first region to the adhesive layer, measured under the conditions of a peeling angle of 30° and a peeling rate of 60 mm/min at a temperature of 23°C) is from the viewpoint of achieving better pickup properties from the pressure-sensitive adhesive layer , 1.1 to 4.5N/25mm or 1.1 to 3.0N/25mm may be sufficient.

0.2 N/25 mm or more may be sufficient as the adhesive force of the 2nd area|region of the adhesive layer with respect to a stainless substrate from a viewpoint of suppressing ring peeling in a dicing process. In addition, this adhesive force means the peel strength measured under the conditions of 90 degrees peeling angle and 50 mm/min of peeling speed|rate in the temperature of 23 degreeC.

The active energy ray-curable adhesive may contain the (meth)acrylic-type resin which has a functional group which can be chain-polymerized. When such a (meth)acrylic resin is included, the functional group may be at least 1 sort(s) chosen from an acryloyl group and a methacryloyl group, and content of the functional group in (meth)acrylic-type resin is 0.1-1.2 mmol/ may be g.

The active energy ray-curable adhesive may further contain the crosslinking agent. When such a crosslinking agent is further included, 0.1-15 mass % of content of the crosslinking agent with respect to the total mass of an active energy ray hardening-type adhesive may be sufficient. The crosslinking 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 hydroxyl groups in one molecule.

The irradiation amount of the active energy ray may be 10-1000 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 of manufacturing a dicing die-bonding integrated film. This manufacturing method comprises the process of producing on the surface of a base material layer, the adhesive layer which consists of an active energy ray-curable adhesive, and the adhesive bond layer formed on the surface of the adhesive layer, The adhesive layer contained in a laminated body The process of irradiating an active energy ray to the area|region used as the 1st area|region of is provided in this order.

One aspect of the present disclosure relates to a method of manufacturing a semiconductor device. This manufacturing method includes the steps of preparing the dicing and die-bonding integrated film, attaching the wafer to the adhesive layer of the dicing and die-bonding integrated film, and attaching a dicing ring to the second surface of the pressure-sensitive adhesive layer A step of dividing the wafer into a plurality of chips, a step of picking up the chip from the pressure-sensitive adhesive layer together with an adhesive piece formed by dividing the adhesive layer into pieces, and a step of placing the chip on a substrate or other chip through the adhesive piece. It has a process of mounting to the.

That is, in this manufacturing method, 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 substrate layer and a second surface opposite to the first surface, and the second surface of the pressure-sensitive adhesive layer A step of preparing a dicing and die-bonding integrated film having an adhesive layer provided to cover the central portion of the dicing and die-bonding integrated film, and attaching the wafer to the adhesive layer of the dicing and die-bonding integrated film, and the second surface of the pressure-sensitive adhesive layer A step of attaching a dicing ring, a step of dividing the wafer into a plurality of chips, a step of picking up the chip from the pressure-sensitive adhesive layer together with an adhesive piece formed by dividing the adhesive layer into pieces; and mounting on a substrate or other chip. The pressure-sensitive adhesive layer has a first region corresponding to the region to which the wafer is affixed in the adhesive layer, and a second region corresponding to the region to which the dicing ring is affixed, and the first region is irradiated with active energy rays, It is a region in a state in which the adhesive force is lowered compared to the second region. In the pressure-sensitive adhesive layer, the adhesive force of the first region of the pressure-sensitive adhesive layer to the adhesive layer, measured under the conditions of a peeling angle of 30° and a peeling rate of 60 mm/min at a temperature of 23° C., is f1 (N/25 mm), at a temperature of 23° C. The difference between f2 and f1 (f2-f1) when the adhesive force of the second region of the pressure-sensitive adhesive layer to the adhesive layer measured under the conditions of a peeling angle of 30° and a peeling rate of 60 mm/min is f2 (N/25 mm) Silver, 6.5~9.0N/25mm.

According to the present disclosure, a dicing die provided with a pressure-sensitive adhesive layer that is applicable to a semiconductor device manufacturing process including a step of dividing a wafer into a plurality of small chips (area 0.1-9 mm ² ) and has excellent pick-up properties. A bonding-integrated film and a method for manufacturing the same are provided. Further, according to the present disclosure, a method for manufacturing a semiconductor device using such a dicing and die-bonding integrated film is provided.

Fig. 1 (a) is a plan view showing one embodiment of a dicing and die-bonding integrated film, and Fig. 1 (b) is a schematic cross-sectional view taken along line BB shown in Fig. 1 (a).
It is a schematic diagram which shows the state by which the dicing ring was affixed on the periphery of the adhesive layer of the dicing die-bonding integrated film, and the wafer was affixed on the surface of the adhesive bond layer.
3 : is sectional drawing which shows typically a mode that the 30 degree peeling strength of the adhesive layer with respect to an adhesive bond layer is being measured.
4 is a schematic cross-sectional view of an embodiment of a semiconductor device.
Fig. 5 (a), Fig. 5 (b), Fig. 5 (c), and Fig. 5 (d) are cross-sectional views schematically showing a process of manufacturing a DAF (a laminate of a chip and an adhesive piece). .
6 is a cross-sectional view schematically illustrating a process of manufacturing the semiconductor device shown in FIG. 4 .
FIG. 7 is a cross-sectional view schematically illustrating a process of manufacturing the semiconductor device shown in FIG. 4 .
FIG. 8 is a cross-sectional view schematically illustrating a process of manufacturing the semiconductor device shown in FIG. 4 .
9 : (a), FIG.9(b), and FIG.9(c) are sectional drawing which shows typically the process of measuring edge peeling strength.
Fig. 10 is a graph showing an example of the relationship between displacement (mm) due to press fit and press force (N).
Fig. 11 is a plan view schematically showing a state in which a mark is placed at a position corresponding to the central portion of a chip to be measured.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this indication is described in detail, referring drawings. In the following description, the same code|symbol is attached|subjected to the same or equivalent part, and the overlapping description is abbreviate|omitted. In addition, this invention is not limited to the following embodiment. In this specification, (meth)acryl means acryl or methacryl, and other analogous expressions, such as (meth)acrylate, are also the same.

<Dicing and die-bonding integrated film>

Fig. 1 (a) is a plan view showing the dicing and die-bonding integrated film according to the present embodiment, and Fig. 1 (b) is a schematic cross-sectional view taken along line BB in Fig. 1 . The dicing and die-bonding integrated film 10 (hereinafter, simply referred to as “film 10” in some cases) is a process of dividing the wafer W into a plurality of chips having an area of 0.1 to 9 mm ² ( and a subsequent pick-up process) can be used in a semiconductor device manufacturing process (refer to FIGS. 5(c) and 5(d)).

The film 10 is an adhesive layer 3 having a base layer 1 and a first face F1 facing the base layer 1 and a second face F2 opposite to the first face F1. ) and the adhesive layer 5 provided to cover the central part of the 2nd surface F2 of the adhesive layer 3 is provided in this order. In this embodiment, although the aspect in which one laminated body of the adhesive layer 3 and the adhesive bond layer 5 was formed on the square base material layer 1 is illustrated, the base material layer 1 has a predetermined length (for example, For example, 100 m or more), and the laminated body of the adhesive layer 3 and the adhesive bond layer 5 may be arrange|positioned at predetermined intervals so that it may be aligned in the longitudinal direction.

(Adhesive layer)

The adhesive layer 3 surrounds the 1st area|region 3a which contains at least the area|region Rw corresponding to the pasting position of the wafer W in the adhesive bond layer 5, and the 1st area|region 3a. a second region 3b located therein. The broken line in FIG.1(a) and FIG.1(b) shows the boundary of the 1st area|region 3a and the 2nd area|region 3b. The 1st area|region 3a and the 2nd area|region 3b consist of the same composition (active energy ray hardening-type adhesive) before irradiation of an active energy ray. The 1st area|region 3a is an area|region in the state in which adhesive force fell compared with the 2nd area|region 3b by irradiating an active energy ray. The 2nd area|region 3b is the area|region to which the dicing ring DR is pasted (refer FIG. 2). The second region 3b is a region not irradiated with an active energy ray, and has a high adhesive force to the dicing ring DR. At least 1 type selected from an ultraviolet-ray, an electron beam, and a visible light ray may be sufficient as an active energy ray, and an ultraviolet-ray may be sufficient as it. The irradiation amount of the active energy ray may be, for example, 10-1000 mJ/cm ² , 100-700 mJ/cm ² , or 200-500 mJ/cm ² .

The adhesive force of the first region 3a of the adhesive layer 3 to the adhesive layer 5 is f1 (N/25mm), and the adhesive force of the second region 3b of the adhesive layer 3 to the adhesive layer 5 is is f2 (N/25mm), the difference (f2-f1) between f2 and f1 is 6.5 to 9.0N/25mm, and may be 7.0 to 9.0N/25mm. Here, f1 and f2 are the 30 degree peeling strengths measured on the conditions of 30 degrees peeling angle and 60 mm/min of peeling rates in the temperature of 23 degreeC. 3 : is sectional drawing which shows typically a mode that the 30 degree peeling strength of the adhesive layer 3 is being measured in the state which fixed the adhesive bond layer 5 of a measurement sample (25 mm width x length 100 mm) to the support plate 80. to be. 3 may be a state in which f1 is being measured. The 2nd area|region 3b of the adhesive layer 3 is the area|region of the same state as the adhesive layer before irradiation of an active energy ray, and can also be called an active energy ray non-irradiation area|region. Therefore, f2 may be measured by replacing the adhesive layer 3 in FIG. 3 with the adhesive layer 3 which does not have the 1st area|region 3a. Since the state of the adhesive layer 3 which does not have the 1st area|region 3a is a state before irradiating an active energy ray with respect to an adhesive layer, f2 is, for example, on the surface of the base material layer 1 , Using a laminate comprising a pressure-sensitive 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, before irradiation with active energy rays, the pressure-sensitive adhesive layer for the adhesive layer (5) 1 It can obtain|require by measuring the adhesive force of the adhesive layer 3) which does not have the area|region 3a. By setting (f2-f1) to such a range, the step of dividing the wafer into a plurality of small chips (area 0.1 to 9 mm ² ) in terms of suppressing cure shrinkage of the pressure-sensitive adhesive layer and reducing the edge peel strength. It is applicable to the manufacturing process of the semiconductor device containing, and the outstanding pick-up property from the adhesive layer 3 can be achieved. (f2-f1) may be 6.6N/25mm or more, 6.8N/25mm or more, 7.0N/25mm or more, or 7.2N/25mm or more, and 8.8N/25mm or less, 8.6N/25mm or less, 8.4N/25mm or less Or less, or 8.2N/25mm or less may be sufficient.

As described above, the film 10 can also be suitably used in a semiconductor device manufacturing process including a step of segmenting a wafer into a plurality of small chips having an area of 0.1 to 9 mm ² (and a step of picking up thereafter). . The present inventors paid attention to 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 of, for example, a size of 8 mm × 6 mm or less. The difference (f2-f1) between the adhesive force of the second region 3b of the pressure-sensitive adhesive layer 3 to the layer 5 and the adhesive force of the first region 3a of the pressure-sensitive adhesive layer 3 to the adhesive layer 5 is It was specified to 6.5-9.0N/25mm. The present inventors have so far found that, with small chips, edge peeling is the dominant factor in pickup properties, and curing shrinkage is the main cause of the increase in edge peeling strength, and (f2-f1) is 6.5 to 9.0N/25mm. By doing so, cure shrinkage could be suppressed and it discovered further that the outstanding pick-up property from the adhesive layer 3 could be achieved. Thereby, by using the film 10, it becomes possible to manufacture a semiconductor device with a sufficiently high yield.

The adhesive force f1 of the 1st area|region 3a of the adhesive layer 3 with respect to the adhesive bond layer 5 may be 1.1-4.5N/25mm or 1.1-3.0N/25mm, for example. 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, 3.2N/25mm or less, or 3.0 N/25mm or less may be sufficient.

The 1st area|region 3a which has the adhesive force of the said range with respect to the adhesive bond layer 5 is formed by irradiation of an active energy ray, and can also be called an active energy ray irradiation area. The present inventors also discovered that reducing the adhesive force of an adhesive layer by irradiation of an active energy ray affects peeling of the edge part of DAF. That is, if the adhesive force of the first region 3a is excessively lowered by irradiation with active energy rays, the 30° peel strength of the first region 3a with respect to the adhesive layer 5 is lowered, while the pickup target is small. In the case of a chip, the edge portion of the DAF tends to be difficult to peel, and the chip is excessively deformed to easily cause cracks or pick-up errors. The lower limit (for example, 1.1 N/25 mm) of the adhesive force of the first region 3a with respect to the adhesive layer 5 can be said to be one that does not excessively decrease the adhesive force before irradiation with an active energy ray, Thereby, even a small chip|tip makes it easy to generate|occur|produce peeling of the edge part of DAF. On the other hand, when the adhesive force of the 1st area|region 3a with respect to the adhesive bond layer 5 is an excessively high thing, there exists a tendency for pick-up property to fall. It is said that the upper limit (for example, 4.5 N/25 mm) of the adhesive force of the first region 3a to the adhesive layer 5 is to reduce the adhesive force before irradiation with an active energy ray to the extent that excellent pick-up properties are expressed. can

The adhesive force f2 of the 2nd area|region 3b of the adhesive layer 3 with respect to the adhesive bond layer 5 may be 8.0-11.5 N/25mm, for example. f2 may be 8.5N/25mm or more, 9.0N/25mm or more, or 9.5N/25mm or more, and 11.0N/25mm or less, 10.8N/25mm or less, or 10.5N/25mm or less may be sufficient as it.

In this embodiment, for example, by adjusting the content of the chain-polymerizable functional group in the (meth)acrylic resin (content of the functional group-introducing compound), the content of the crosslinking agent in the pressure-sensitive adhesive layer, and the amount of active energy ray irradiation, or , for example, f1, f2, and (f2-f1) can be adjusted by adding other resins (such as acrylic monomers or oligomers, urethane monomers or oligomers) or tackifiers (such as tachifiers).

The adhesive force of the 2nd area|region 3b of the adhesive bond layer 3 with respect to a stainless steel substrate may be 0.2 N/25 mm or more. This adhesive force is a 90 degree peeling strength measured on the conditions of 90 degrees peeling angle and 50 mm/min of peeling rates in the temperature of 23 degreeC. When this adhesive force is 0.2 N/25 mm or more, ring peeling at the time of dicing can fully be suppressed. The adhesive force of the 2nd area|region 3b of the adhesive layer 3 with respect to a stainless steel substrate may be 0.25 N/25 mm or more or 0.3 N/25 mm or more, and 2.0 N/25 mm or less, 1.0 N/25 mm or less, 0.8 N/25 mm or less. or less, or 0.6 N/25 mm or less may be sufficient.

The adhesive layer before irradiation of an active energy ray consists of an active energy ray hardening-type adhesive containing a (meth)acrylic-type resin, a photoinitiator, and a crosslinking agent, for example. The second region 3b to which the active energy ray is not irradiated may have the same composition as the pressure-sensitive adhesive layer before irradiating the active energy ray. Hereinafter, the components contained in an active energy ray hardening-type adhesive are demonstrated in detail.

[(meth)acrylic resin]

The active energy ray-curable adhesive may contain the (meth)acrylic-type resin which has a functional group which can be chain-polymerized. When such a (meth)acrylic-type resin is included, the at least 1 sort(s) chosen from an acryloyl group and a methacryloyl group may be sufficient as a functional group. 0.1-1.2 mmol/g may be sufficient as content of the functional group in (meth)acrylic-type resin. 0.2 mmol/g or more or 0.3 mmol/g or more may be sufficient as content of the functional group in (meth)acrylic-type resin, and 1.0 mmol/g or less, 0.8 mmol/g or less, 0.7 mmol/g or less, 0.6 mmol/g or less , or 0.5 mmol/g or less may be sufficient. When the content of the functional group is 0.1 mmol/g or more, there is a tendency to easily form a region (the first region 3a) in which the adhesive force is appropriately lowered by irradiation with active energy ray, and on the other hand, when it is 1.2 mmol/g or less, excellent It tends to be easy to achieve pickup properties.

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 bulk polymerization method, a precipitation polymerization method, a gas phase polymerization method, a plasma polymerization method, and a supercritical polymerization method. can Examples of the polymerization reaction include radical polymerization, cationic polymerization, anionic polymerization, living radical polymerization, living cationic polymerization, living anionic polymerization, coordination polymerization, immortal polymerization, etc., ATRP (atom transfer radical polymerization) and RAFT (reversible addition cleavage) chain transfer polymerization) can also be mentioned. Among these, synthesis by radical polymerization using the solution polymerization method has advantages such as good economic feasibility, high reaction rate, ease of polymerization control, and the like, as well as being able to blend the resin solution obtained by polymerization as it is.

Here, the method of obtaining a (meth)acrylic-type resin by radical polymerization using a solution polymerization method is taken as an example, and the synthesis method of a (meth)acrylic-type resin is demonstrated in detail.

As a monomer used when synthesize|combining (meth)acrylic-type resin, if it has one (meth)acryloyl group in 1 molecule, there will be no restriction|limiting in particular. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, butoxyethyl (meth) acrylate , 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 (meth)acrylate, methoxypolypropylene glycol aliphatic (meth)acrylates such as (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, and mono(2-(meth)acryloyloxyethyl)succinate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) alicyclic (meth)acrylates such as acrylate, mono(2-(meth)acryloyloxyethyl)tetrahydrophthalate, and mono(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, phenoxy Cypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, phenoxypolypropylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth) Acrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl (meth)acrylate, 2-hydroxy-3-(1-naphthoxy)propyl (meth)acrylate, 2-hydroxy-3 Aromatic (meth)acrylates, such as -(2-naphthoxy)propyl (meth)acrylate; Heterocyclic (meth), such as 2-tetrahydrofurfuryl (meth)acrylate, N-(meth)acryloyloxyethyl hexahydrophthalimide, and 2-(meth)acryloyloxyethyl-N-carbazole ) acrylates, caprolactone-modified products thereof, ω-carboxy-polycaprolactone mono (meth) acrylate, glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, α-propyl glycidyl Cydyl (meth) acrylate, α-butyl glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 2-ethyl glycidyl (meth) acrylate, 2-propyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxyheptyl (meth)acrylate, α-ethyl-6,7-epoxyheptyl (meth)acrylate, 3,4- compounds having an ethylenically unsaturated group and an epoxy group, such as epoxycyclohexylmethyl (meth)acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; (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-(2 a compound having an ethylenically unsaturated group and an oxetanyl group, such as -methyl-2-oxetanyl)propyl (meth)acrylate; compounds having an ethylenically unsaturated group and an isocyanate group such as 2-(meth)acryloyloxyethyl isocyanate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2- The compound which has ethylenically unsaturated groups, such as hydroxybutyl (meth)acrylate, and a hydroxyl group is mentioned. By combining these suitably, the target (meth)acrylic-type resin can be obtained.

The (meth)acrylic resin may have at least one functional group selected from a hydroxyl group, a glycidyl group (epoxy group), an amino group, and the like as a reaction point with a functional group-introducing compound or crosslinking agent described later. As a monomer for synthesizing (meth)acrylic resin having a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acryl The compound etc. which have ethylenically unsaturated groups, such as a rate, 3-chloro-2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate, and a hydroxyl group are mentioned. These may be used individually by 1 type or may use 2 or more types together.

As a monomer for synthesizing a (meth)acrylic resin having a glycidyl group, glycidyl (meth)acrylate, α-ethylglycidyl (meth)acrylate, α-propylglycidyl (meth)acrylate, α-butyl glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, 2-ethyl glycidyl (meth) acrylate, 2-propyl glycidyl (meth) acrylate, 3, 4-epoxybutyl (meth)acrylate, 3,4-epoxyheptyl (meth)acrylate, α-ethyl-6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acryl and compounds having an ethylenically unsaturated group and an epoxy group, such as lactate, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether. These may be used individually by 1 type or may use 2 or more types together.

The (meth)acrylic-type resin synthesize|combined from these monomers contains the functional group which can be chain-polymerized. The functional group capable of chain polymerization is at least one selected from, for example, 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 (epoxy group), an amino group, and the like synthesized as described above, and the following compound (functional group introduction) compound), it can introduce|transduce in the said (meth)acrylic-type resin. Specific examples of the functional group-introducing compound include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate cyanate, 1,1-(bisacryloyloxymethyl)ethylisocyanate; Acryloyl monoisocyanate compound obtained by reaction of a diisocyanate compound or a polyisocyanate compound, and hydroxyethyl (meth)acrylate or 4-hydroxybutylethyl (meth)acrylate; The acryloyl monoisocyanate compound etc. which are obtained by reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate are mentioned. These may be used individually by 1 type or may use 2 or more types together. Among these, the functional group-introducing compound may be 2-methacryloyloxyethyl isocyanate.

[Photoinitiator]

There is no restriction|limiting in particular as long as a photoinitiator generate|occur|produces the active species which can be chain-polymerized by irradiating an active energy ray. At least 1 type selected from an ultraviolet-ray, an electron beam, and a visible light ray may be sufficient as an active energy ray, and an ultraviolet-ray may be sufficient as it. As a photoinitiator, a photoradical polymerization initiator etc. are mentioned, for example. Here, the active species capable of chain polymerization means that a polymerization reaction is initiated by reacting with a functional group capable of chain polymerization.

As a photo-radical polymerization initiator, For example, benzoin ketals, such as 2, 2- dimethoxy-1,2- diphenylethan-1-one; 1-Hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2- α-hydroxyketones such as methyl-1-propan-1-one; 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 1,2-methyl-1-[4-(methylthio)phenyl]-2-morphopoly α-aminoketones such as nopropan-1-one; oxime esters such as 1-[4-(phenylthio)phenyl]-1,2-octadione-2-(benzoyl)oxime; Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethyl Phosphine oxides, such as a benzoyl diphenyl phosphine 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-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4 2,4,5-triaryl imidazole dimers, such as a , 5- diphenyl imidazole dimer; Benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylamino benzophenone compounds such as benzophenone; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di Phenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethyl quinone compounds such as anthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; benzyl compounds such as benzyldimethyl ketal; Acridine compounds, such as 9-phenylacridine and 1,7-bis (9,9'- acridinyl heptane): N-phenylglycine, coumarin, etc. are mentioned.

0.1-30 mass parts, 0.3-10 mass parts, or 0.5-5 mass parts may be sufficient as content of the photoinitiator in an active energy ray hardening-type adhesive with respect to content 100 mass parts of (meth)acrylic-type resin. When content of a photoinitiator is 0.1 mass part or more, hardening becomes enough after an adhesive layer irradiation with an active energy ray, and there exists a tendency for a pickup defect to occur easily. When content of a photoinitiator is 30 mass parts or less, there exists a tendency which can prevent the contamination with respect to an adhesive bond layer (transfer to the adhesive bond layer of a photoinitiator).

[crosslinking agent]

A crosslinking agent is used for the purpose of controlling the elastic modulus and/or adhesiveness of an adhesive layer, for example. The crosslinking agent may be a compound having two or more functional groups capable of reacting with at least one functional group selected from a hydroxyl group, a glycidyl group, an amino group, and the like of the (meth)acrylic resin in one molecule. As a bond formed by reaction of a crosslinking agent and (meth)acrylic-type resin, an ester bond, an ether bond, an amide bond, an imide bond, a urethane bond, a urea bond, etc. are mentioned, for example.

In the present embodiment, the crosslinking 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 easily reacts with the hydroxyl group, glycidyl group, amino group, etc. which the (meth)acrylic-type resin has, and can 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, 1,4-xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diiso Cyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, Isocyanate compounds, such as dicyclohexylmethane-2,4'- diisocyanate and lysine isocyanate, etc. are mentioned.

The crosslinking agent may be a reaction product of a polyfunctional isocyanate and a polyhydric alcohol having two or more hydroxyl groups in one molecule (isocyanate group-containing oligomer). Examples of the polyhydric alcohol having two or more hydroxyl groups in one molecule include ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, 1,8-octanediol. , 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecaindiol, glycerin, trimethylolpropane, pentaerythritol, diol Pentaerythritol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, etc. are mentioned.

Among these, the crosslinking 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 hydroxyl groups in one molecule (isocyanate group-containing oligomer). do. By using such an isocyanate group-containing oligomer as a crosslinking agent, the pressure-sensitive adhesive layer 3 forms a dense crosslinked structure, thereby sufficiently suppressing adhesion of the pressure-sensitive adhesive to the adhesive layer 5 in the pickup process. tends to

Content of the crosslinking agent in an active energy ray hardening-type adhesive can be suitably set according to the cohesive force calculated|required with respect to an adhesive layer, elongation at break, adhesiveness with an adhesive bond layer, etc. Specifically, 3-30 mass parts, 4-15 mass parts, or 7-10 mass parts may be sufficient as content of a crosslinking agent with respect to content 100 mass parts of (meth)acrylic-type resin. By making the content of the crosslinking agent in the above range, it is possible to achieve good balance between the properties required for the pressure-sensitive adhesive layer in the dicing process and the properties required for the pressure-sensitive adhesive layer in the die bonding step, and excellent pick-up properties can also be achieved. have.

If the content of the crosslinking 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 crosslinked structure is unlikely to be insufficient, and in the pickup step, the interfacial adhesion with the adhesive layer is sufficiently reduced, so that at the time of pickup Defects tend to be less likely to occur. On the other hand, when content of a crosslinking agent is 30 mass parts or more with respect to content of 100 mass parts of (meth)acrylic-type resin, an adhesive layer is hard to become hard too much, and there exists a tendency for a chip|tip to be hard to peel in an expand process.

Content of the crosslinking agent with respect to the total mass of an active energy ray hardening-type adhesive may be 0.1-15 mass %, 3-15 mass %, or 5-15 mass %, for example. When the content of the crosslinking agent is 0.1% by mass or more, it is easy to form a region (the first region 3a) in which the adhesive force is appropriately lowered by irradiation with active energy rays, and on the other hand, when it is 15% by mass or less, excellent pickup properties are achieved. tends to be easy.

What is necessary is just to set the thickness of the adhesive layer 3 suitably according to the conditions (temperature, tension|tensile_strength, etc.) of an expand process, for example, 1-200 micrometers, 5-50 micrometers, or 10-20 micrometers may be sufficient. 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 cuff width becomes wide at the time of expansion (stress is not relieved at the time of pushing up the pin), and the pickup becomes insufficient. tends to be difficult.

The adhesive layer 3 is formed on the base material layer 1 . As a formation method of the adhesive layer 3, the known method is employable. For example, the laminate of the base material layer 1 and the adhesive layer 3 may be formed by the two-layer extrusion method, the varnish (varnish for adhesive layer formation) of an active energy ray hardening type adhesive is prepared, and this is a base material layer It may be coated on the surface of (1), or the adhesive layer 3 may be formed on the film by which the release process was carried out, and this may be transcribe|transferred to the base material layer 1.

The varnish (varnish for adhesive layer formation) of an active energy ray hardening type adhesive is an organic solvent which can melt|dissolve (meth)acrylic-type resin, a photoinitiator, and a crosslinking agent, and may volatilize by heating. Specific examples of the organic solvent include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-cymene; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, and propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; carbonate 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 mono Methyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether polyhydric alcohol alkyl ethers such as , diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, polyhydric alcohol alkyl ether acetates such as diethylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate; and amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. These organic solvents may be used individually by 1 type, and may use 2 or more types together.

Among these, from the viewpoint of solubility and boiling point, the organic solvent is, for example, toluene, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate. , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, ethylene glycol At least one selected from the group consisting of cholmonomethyl ether acetate, propylene glycol monomethyl ether acetate, and N,N-dimethylacetamide may be sufficient. Solid content concentration of a varnish is 10-60 mass % normally.

(substrate layer)

A known polymer sheet or film can be used for the base material layer 1, and on low-temperature conditions, if an expand process can be implemented, it will not restrict|limit especially. Specific examples of the substrate 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 copolymer, poly oil Polyester such as lethane, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyetheretherketone, polyimide, polyetherimide, polyamide, wholly aromatic polyamide, polyphenylsulfide, aramid ( paper), glass, glass fiber, fluororesin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, silicone resin, or a mixture of these with a plasticizer, or a cured product crosslinked by electron beam irradiation. can be heard

The base layer 1 has a surface mainly comprising at least one resin selected from the group consisting of polyethylene, polypropylene, polyethylene-polypropylene random copolymer, and polyethylene-polypropylene block copolymer, and the surface and The adhesive layer 3 may be in contact. These resins can serve as good substrates from the viewpoints of characteristics such as Young's modulus, stress relaxation property, melting point, and the like, price, and recycling of waste materials after use. A single layer may be sufficient as the base material layer 1, and it may have a multilayer structure in which the layers which consist of different materials were laminated|stacked as needed. From a viewpoint of controlling adhesiveness with the adhesive layer 3, the base material layer 1 may perform surface roughening processes, such as a matting process and a corona treatment, with respect to the surface.

(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, it is excellent in adhesiveness between chips/substrates and between chips/chips, and it is possible to provide electrode embedding property, wire embedding property, etc., and, in the die bonding process, It tends to have characteristics such as being able to adhere, providing excellent curing in a short time, and having excellent reliability after molding with a sealant.

The reactive group-containing (meth)acrylic copolymer may be, for example, an epoxy group-containing (meth)acrylic copolymer. The copolymer obtained by using glycidyl (meth)acrylate as a raw material in the amount used as 0.5-6 mass % with respect to the copolymer obtained may be sufficient as an epoxy-group containing (meth)acryl copolymer. When content of glycidyl (meth)acrylate is 0.5 mass % or more, it will become easy to obtain high adhesive force, and on the other hand, there exists a tendency which gelation can be suppressed because it is 6 mass % or less. 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, and acrylonite. A reel or the like may be used. Among these, ethyl (meth)acrylate and/or butyl (meth)acrylate may be sufficient as the monomer which comprises the remainder of a reactive group containing (meth)acrylic copolymer. The mixing ratio can be adjusted in consideration of the Tg of the reactive group-containing (meth)acrylic copolymer. If Tg is -10 degreeC or more, it exists in the tendency which can suppress that the tacking property of the adhesive bond layer 5 in a B-stage state becomes large too much, and there exists a tendency excellent in handleability. In addition, the glass transition point (Tg) of an epoxy-group containing (meth)acryl copolymer may be 30 degrees C or less, for example. Although the polymerization method in particular is not restrict|limited, For example, pearl polymerization, solution polymerization, etc. are mentioned. As a commercially available epoxy group-containing (meth)acrylic copolymer, HTR-860P-3 (trade name, manufactured by Nagase Chemtex Co., Ltd.) is mentioned, for example.

From the viewpoints of adhesiveness and heat resistance, the weight average molecular weight of the epoxy group-containing (meth)acryl copolymer may be 100,000 or more, or may be 300,000 to 3,000,000 or 500,000 to 2,000,000. It can suppress that the fillability between a chip|tip and the board|substrate which supports this falls that a weight average molecular weight is 3 million or less. A weight average molecular weight is a polystyrene conversion value using the analytical curve by standard polystyrene by the gel permeation chromatography method (GPC).

As a hardening accelerator, tertiary amine, imidazole, quaternary ammonium salts, etc. are mentioned, for example. Specific examples of the curing accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium tri melitate. These may be used individually by 1 type, and may use 2 or more types together.

An inorganic filler may be sufficient as a 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, boron nitride, crystalline silica, and amorphous silica. can These may be used individually by 1 type, and may use 2 or more types together.

The adhesive composition may further contain an epoxy resin and an epoxy resin curing agent. Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac epoxy resin, cresol novolak epoxy resin, Bisphenol A novolac type epoxy resin, diglycidyl ether of biphenol, diglycidyl ether of naphthalenediol, diglycidyl ether of phenol, diglycidyl ether of alcohol and bifunctional epoxy resins, such as products and their alkyl-substituted products, halides, and hydrogenated substances, and novolak-type epoxy resins. Moreover, you may apply other generally known epoxy resins, such as a polyfunctional epoxy resin and a heterocyclic-containing epoxy resin. These can be used individually or in combination of 2 or more types. Moreover, components other than an epoxy resin may be contained as an impurity in the range which does not impair a characteristic.

As an epoxy resin hardening|curing agent, the phenol resin etc. which can be obtained by making a phenol compound and the xylylene compound which are divalent coupling groups react in presence of a non-catalyst or an acid catalyst are mentioned, for example. As a phenol compound used for manufacture of a phenol resin, For example, phenol, o-cresol, m-cresol, p-cresol, o-ethyl phenol, p-ethyl phenol, o-n-propyl phenol, m-n-propyl phenol, p-n -Propylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, o-n-butylphenol, m-n-butylphenol, p-n-butylphenol, o-isobutylphenol, m-isobutylphenol, p -Isobutylphenol, octylphenol, nonylphenol, 2,4-xyleneol, 2,6-xyleneol, 3,5-xyleneol, 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-bromophenol, p-bromophenol, o-iodophenol, p-iodophenol, o-fluorophenol, m-fluorophenol, p-fluorophenol, etc. can be heard These phenolic compounds may be used independently and may mix and use 2 or more types. As a xylylene compound which is a bivalent linking group used for manufacture of a phenol resin, xylylene dihalide shown below, xylylene diglycol, and its derivative(s) can be used. That is, specific examples of the xylylene 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′-dihydride Roxy-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'-di-isopropoxy-p-xylene, α,α'-diisopropoxy-m-xylene, α,α'-diisopropoxy-o-xyl Ren, 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, α,α'-di-tert-butoxy-o-xylene, etc. can be heard These may be used individually by 1 type or may use 2 or more types together.

When making a phenol compound and a xylylene compound react, mineral acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, and polyphosphoric acid; organic carboxylic acids such as dimethyl sulfuric acid, diethyl sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and ethanesulfonic acid; super strong acids such as trifluoromethanesulfonic acid; strongly acidic ion exchange resins such as an alkanesulfonic acid type ion exchange resin; super acid ion exchange resins such as perfluoroalkanesulfonic acid type ion exchange resins (trade names: Nafion, manufactured by Nafion, Du Pont, "Nafion" is a registered trademark); natural and synthetic zeolites; A phenol resin can be obtained by reacting using an acid catalyst such as activated clay (acid clay) until the xylylene compound, which is a raw material, substantially disappears and the reaction composition becomes constant at 50 to 250°C. The reaction time can be appropriately set depending on the raw materials and the reaction temperature, for example, can be set to 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 bond layer 5 may be 1-300 micrometers, 5-150 micrometers, or 10-100 micrometers, for example. When the thickness of the adhesive layer 5 is 1 µm or more, the adhesiveness is more excellent, and on the other hand, when it is 300 µm or less, there is a tendency that the splitting property and the pick-up property at the time of expansion are more excellent.

<Manufacturing method of dicing die-bonding integrated film>

The manufacturing method of the film 10 is, on the surface of the base material layer 1, an adhesive layer formed of an active energy ray-curable pressure-sensitive adhesive whose adhesive strength is lowered by irradiation with active energy rays, and an adhesive layer formed on the surface of the pressure-sensitive adhesive layer ( The process of producing the laminated body containing 5) and the process of irradiating an active energy ray to the area|region used as the 1st area|region 3a of the adhesive layer contained in a laminated body are provided in this order. The irradiation amount of the active energy ray with respect to the area|region used as the 1st area|region 3a may be 10-1000 mJ/cm< ² >, for example, 100-700 mJ/cm< ² >, or 200-500 mJ/cm< ² > may be sufficient. The said manufacturing method produces the laminated body of an adhesive layer and the adhesive bond layer 5 first, and irradiates an active energy ray to the specific area|region of an adhesive layer after that.

<Semiconductor device and its manufacturing method>

4 is a cross-sectional view schematically showing a semiconductor device according to the present embodiment. The semiconductor device 100 shown in this figure includes a substrate 70 , four chips S1 , S2 , S3 , and S4 stacked on the surface of the substrate 70 , and electrodes ( (not shown), wires W1, W2, W3, and W4 for electrically connecting the four chips S1, S2, S3, and S4, and a sealing layer 50 sealing them.

The substrate 70 may be, for example, an organic substrate, or 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 warpage of the semiconductor device 100 .

The four chips S1, S2, S3, and S4 are laminated through the cured product 5C of the adhesive piece 5P. The shape of the chips S1, S2, S3, and S4 in a plan view is, for example, a square or a rectangle. The area of the chips S1, S2, S3, and 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, and S4 may be, for example, 10 to 170 µm or 25 to 100 µm. Further, 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.

In the manufacturing method of the semiconductor device 100, the process of preparing the above-mentioned film 10, bonding the wafer W with respect to the adhesive bond layer 5 of the film 10, and manufacturing the adhesive layer 3 A step of attaching a dicing ring DR to the two surfaces F2, a step of dividing the wafer W into a plurality of chips S (dicing step), a DAF 8 (a chip S1) and the step of picking up the laminate of the adhesive piece 5P (see Fig. 5(d)) from the first region 3a of the pressure-sensitive adhesive layer 3, and the chip S1 through the adhesive piece 5P , a process of mounting on the substrate 70 is provided.

An example of the manufacturing method of the DAF 8 is demonstrated, referring FIG.5(a), FIG.5(b), FIG.5(c), and FIG.5(d). First, the above-described film 10 is prepared. As shown in FIG.5(a) and FIG.5(b), the film 10 is affixed so that the adhesive bond layer 5 may contact with one surface of the wafer W. As shown in FIG. Moreover, the dicing ring DR is affixed with respect to the 2nd surface F2 of the adhesive layer 3 .

The wafer W, the adhesive layer 5, and the adhesive layer 3 are diced. Thereby, as shown in FIG.5(c), the wafer W is divided into pieces, and it becomes the chip|tip S. As shown in FIG. The adhesive bond layer 5 is also divided into pieces, and it becomes the adhesive bond piece 5P. As a dicing method, the method using a dicing blade or a laser is mentioned. Alternatively, the wafer W may be thinned by grinding the wafer W prior to dicing.

After dicing, without irradiating an active energy ray with respect to the pressure-sensitive adhesive layer 3, as shown in FIG. While separating the adhesive piece 5P from the pressure-sensitive adhesive layer 3 by pushing it up with the pins 42 while being spaced apart from each other, the DAF 8 is sucked up by the suction collet 44 and picked up.

A method of manufacturing the semiconductor device 100 will be described in detail with reference to FIGS. 6 , 7 , and 8 . First, as shown in FIG. 6 , the first-stage chip S1 (chip S) is pressed to a predetermined position on the substrate 70 via the adhesive piece 5P. Next, the adhesive piece 5P is hardened by heating. Thereby, the adhesive bond piece 5P is hardened|cured and it becomes the hardened|cured material 5C. You may perform the hardening process of the adhesive bond piece 5P in a pressurized atmosphere from a viewpoint of reduction of a void.

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

As mentioned above, although embodiment of this indication was described in detail, this invention is not limited to the said embodiment. For example, in the said embodiment, although the film 10 provided with the base material layer 1, the adhesive layer 3, and the adhesive bond layer 5 in this order was illustrated, it is equipped with the adhesive bond layer 5 It may be an aspect not to do. Moreover, the film 10 may further be equipped with the cover film (not shown) which covers the adhesive bond layer 5. As shown in FIG.

Example

Hereinafter, the present disclosure will be described in more detail based on Examples, but the present invention is not limited to these Examples. In addition, unless there is a special description, all chemicals used reagents.

<Production Example 1>

[Synthesis of acrylic resin (A-1)]

The following components were placed in a flask with a capacity of 2000 mL in which a three-one motor, a stirring blade, and a nitrogen introduction tube were installed.

・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 bil parts

After stirring the contents until sufficiently uniform, bubbling was performed 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. for 1 hour, and polymerization was performed for 6 hours after the temperature was raised. Next, the reaction solution is transferred to a pressure cooker with a capacity of 2000 mL installed with a three-one motor, a stirring blade, and a nitrogen inlet tube, heated at 120 ° C and 0.28 MPa for 4.5 hours, and then cooled to room temperature (25 ° C, the same below). did.

Next, 490 mass parts of ethyl acetate was added, it stirred, and the content was diluted. After adding 0.10 mass parts of dioctyl tin dilaurate to this as a urethanization catalyst, 2-methacryloyloxyethyl isocyanate (The Showa Denko Co., Ltd. make, Karenz MOI (brand name)) was added After adding 48.6 mass parts and making it react at 70 degreeC for 6 hours, it cooled to room temperature. Subsequently, ethyl acetate was further added, and the nonvolatile matter content in the acrylic resin solution was adjusted to be 35 mass %, and a solution containing the acrylic resin (A-1) having a functional group capable of chain polymerization of Production Example 1 was obtained.

The solution containing the acrylic resin (A-1) obtained as mentioned above was vacuum-dried at 60 degreeC overnight. The solid content thus obtained was subjected to elemental analysis with a fully automatic elemental analyzer (manufactured by Elementa, trade name: varioEL), and the content of the functional group derived from the introduced 2-methacryloxyethyl isocyanate was calculated from the nitrogen content. As a result, 0.50 mmol/g.

Moreover, the weight average molecular weight of polystyrene conversion of acrylic resin (A-1) was calculated|required using the following apparatus. That is, SD-8022/DP-8020/RI-8020 manufactured by Tosoh Corporation was used, and Gelpack GL-A150-S/GL-A160-S manufactured by Hitachi Kasei Corporation was used for the column, and tetrahydrofuran was used as the eluent. GPC measurements were performed. As a result, the weight average molecular weight in terms of polystyrene was 800,000. The hydroxyl value and acid value measured based on the method of JISK0070 were 56.1 mgKOH/g and 6.5 mgKOH/g. These results are put together in Table 1, and are shown.

<Production Example 2>

[Synthesis of acrylic resin (A-2)]

Except for changing the raw material monomer composition shown in Production Example 1 in Table 1 to the raw monomer composition shown in Production Example 2 in Table 1, in the same manner as in Production Example 1, containing the acrylic resin (A-2) of Production Example 2 A solution was obtained. Table 1 shows the measurement results of the properties of the acrylic resin (A-2) of Production Example 2.

<Production Example 3>

[Synthesis of acrylic resin (A-3)]

Except for changing the raw material monomer composition shown in Production Example 1 in Table 1 to the raw monomer composition shown in Production Example 3 in Table 1, in the same manner as in Production Example 1, containing the acrylic resin (A-3) of Production Example 3 A solution was obtained. Table 1 shows the measurement results of the properties of the acrylic resin (A-3) of Production Example 3.

[Table 1]

<Example 1>

[Production of dicing film (adhesive layer)]

By mixing the following components, the varnish (varnish for adhesive layer formation) of an active energy ray hardening-type adhesive was prepared (refer Table 2). The quantity of ethyl acetate (solvent) was adjusted so that the total solid content of a varnish might be 25 mass %.

- Solution containing acrylic resin (A-1) of Production Example 1: 100 parts by mass (solid content)

-Photoinitiator (B-1) (1-hydroxycyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, Irgacure 184, "Irgacure" is a registered trademark): 1.0 mass part

Crosslinking agent (C-1) (polyfunctional isocyanate (reactant of tolylene diisocyanate and trimethylol propane), manufactured by Nippon Polyurethane Kogyo Co., Ltd., Colonate L, solid content: 75%) : 8.0 parts by mass (solid content)

・Ethyl acetate (solvent)

The polyethylene terephthalate film (450 mm in width, 500 mm in length, 38 micrometers in thickness) to which the mold release process was given to one surface was prepared. After apply|coating the varnish of the active energy ray hardening type adhesive to the surface to which the mold release process was performed using the applicator, it dried at 80 degreeC for 5 minutes. Thereby, the laminated body (dicing film) which consists of a polyethylene terephthalate film and the 30 micrometers-thick adhesive layer formed thereon was obtained.

The polyolefin film (450 mm in width, 500 mm in length, 80 micrometers in thickness) to which the corona treatment was given to one surface was prepared. The surface to which the corona treatment was given and the adhesive layer of the said laminated body were bonded together at room temperature. Next, the pressure-sensitive adhesive layer was transferred to the polyolefin film (cover film) by pressing with a rubber roll. Then, the dicing film with a cover film was obtained by leaving it to stand at room temperature for 3 days.

[Production of die bonding film (adhesive layer)]

By mixing the following components, the varnish for adhesive bond layer formation was prepared. First, with respect to the mixture containing the following components, cyclohexanone (solvent) was added, and after stirring and mixing, it further kneaded using the bead mill for 90 minutes.

・Epoxy resin (YDCN-700-10 (trade name), manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., cresol novolak type epoxy resin, epoxy equivalent: 210, molecular weight: 1200, softening point: 80°C): 14 parts by mass

-Phenolic resin (Milex XLC-LL (trade name), Mitsui Chemicals Co., Ltd. make, phenol resin, hydroxyl equivalent: 175, water absorption: 1.8%, heating weight loss rate at 350 degreeC: 4%): 23 mass parts

· Silane coupling agent (NUC A-189 (trade name), manufactured by NUC Corporation, γ-mercaptopropyl trimethoxysilane): 0.2 parts by mass

· Silane coupling agent (NUCA-1160 (trade name), manufactured by Nippon Unica 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 adding the following components to the mixture obtained as described above, a varnish for forming an adhesive layer (at least a reactive group-containing (meth)acrylic copolymer, a curing accelerator, and a filler through the steps of stirring and mixing and vacuum degassing) varnish of the adhesive composition) was obtained.

・Epoxy group-containing acrylic copolymer (HTR-860P-3 (trade name), manufactured by Nagase Chemtex Co., Ltd., weight average molecular weight: 800,000): 16 parts by mass

-Cure accelerator (Curesol 2PZ-CN (trade name), Shikoku Kasei Kogyo Co., Ltd. make, 1-cyanoethyl-2-phenylimidazole, "Curesol" is a registered trademark): 0.1 mass part

The polyethylene terephthalate film (thickness 35 micrometers) to which the mold release process was given to one surface was prepared. After apply|coating the varnish for adhesive bond layer formation to the surface to which the mold release process was performed using the applicator, it heat-dried at 140 degreeC for 5 minutes. Thereby, the laminated body (die-bonding film) which consists of a polyethylene terephthalate film (carrier film) and the 25-micrometer-thick adhesive bond layer (B-stage state) formed thereon was obtained.

[Production of dicing and die-bonding integrated film]

The die-bonding film which consists of an adhesive bond layer and a carrier film was cut circularly with a diameter of 335 mm for every carrier film. After sticking the dicing film which peeled the polyethylene terephthalate film to the cut die-bonding film at room temperature, it was left to stand at room temperature for 1 day. Thereafter, the dicing film was cut into a circular shape with a diameter of 370 mm to obtain a laminate. Thus, the ultraviolet-ray was irradiated as follows to the area|region (1st area|region of an adhesive layer) corresponding to the sticking position of the wafer in the adhesive bond layer of the obtained laminated body. That is, using a pulsed xenon lamp, ultraviolet rays were partially irradiated with an irradiation amount of 70 W and 300 mJ/cm ² . In addition, ultraviolet irradiation was performed with respect to the part with an inner diameter of 318 mm from the center of a film using a dark film. In this way, a plurality of dicing and die-bonding integrated films of Example 1 for use in various evaluation tests described later were obtained.

<Example 2>

Except having changed the irradiation amount of ultraviolet rays from 300 mJ/cm ² to 200 mJ/cm ² , it was carried out in the same manner as in Example 1 to obtain a plurality of dicing and die-bonding integrated films of Example 2.

<Example 3>

Except having changed the irradiation amount of ultraviolet rays from 300 mJ/cm ² to 500 mJ/cm ² , it was carried out in the same manner as in Example 1 to obtain a plurality of dicing and die-bonding integrated films of Example 3.

<Example 4>

Photoinitiator (B-2) (2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)) for the photoinitiator (B-1) used when producing the dicing film -Benzyl]-phenyl}-2-methyl-propan-1-one, manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 127, "Irgacure" is a registered trademark))) Same as in Example 1 Thus, a plurality of dicing and die-bonding integrated films of Example 4 were obtained.

<Example 5>

In the same manner as in Example 3, except that the acrylic resin (A-1) used for producing the dicing film was changed to the acrylic resin (A-2), a plurality of dicing and die-bonding integrated films of Example 5 got

<Comparative Example 1>

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), the dicing and die-bonding integrated films of Comparative Examples 1 got

[Evaluation Test]

(1) Measurement of the adhesive force (30° peel strength) of the pressure-sensitive adhesive layer to the adhesive layer

The adhesive force (f1) of the 1st area|region of the adhesive layer with respect to an adhesive bond layer, and the adhesive force (f2) of the 2nd area|region of the adhesive layer with respect to an adhesive bond layer were evaluated by measuring the 30 degree peeling strength. In addition, f1 corresponds to the adhesive force of the 1st area|region of the adhesive layer after irradiation of ultraviolet-ray to the adhesive bond layer, and f2 corresponds to the adhesive force of the area|region used as the 1st area|region of the adhesive layer before irradiation of ultraviolet-ray to the adhesive bond layer. . Therefore, f1 uses the dicing and die-bonding integrated film after irradiation with ultraviolet rays in [Preparation of dicing and die-bonding integrated film], and f2 is the adhesive force ( 30° peel strength) was measured. The measurement sample was obtained by preparing a dicing and die-bonding integrated film and a laminate, and cutting them out to 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 of the first area of the pressure-sensitive adhesive layer after irradiation with ultraviolet light to the adhesive layer from each measurement sample and the UV light to the adhesive layer The peeling strength (peel strength of the 2nd area|region of the adhesive layer with respect to an adhesive layer) of the area|region used as the 1st area|region of the adhesive layer before irradiation was measured. Measurement conditions were made into 30 degrees of peeling angle, and 60 mm/min of peeling rates. In addition, the storage of a sample and the measurement of the peeling strength were performed in the environment of the temperature of 23 degreeC, and 40% of relative humidity. A result is shown in Table 2.

(2) Measurement of the adhesive force (90° peel strength) of the pressure-sensitive adhesive layer to the stainless steel substrate

The adhesive force of the 2nd area|region of the adhesive layer with respect to a stainless steel board|substrate was evaluated by measuring a 90 degree peeling strength. In addition, the said adhesive force corresponds to the adhesive force of the adhesive layer before irradiation of the ultraviolet-ray with respect to a stainless steel substrate. Therefore, the said adhesive force measured adhesive force (90 degree peeling strength) using the laminated body before irradiation of the ultraviolet-ray in [Preparation of a dicing die-bonding integrated film]. The measurement sample was obtained by preparing a laminated body, cutting out this to 25 mm in width and 100 mm in length, and affixing the surface by the side of an adhesive layer to a stainless steel substrate (SUS430BA). The peeling strength of the adhesive layer with respect to a stainless steel substrate was measured from the measurement sample using the tensile tester (The Shimadzu Corporation make, autograph "AGS-1000"). The measurement conditions were a peeling angle of 90° and a peeling rate of 50 mm/min. A result is shown in Table 2.

(3) Measurement of cure shrinkage of the pressure-sensitive adhesive layer

Two polyethylene terephthalate films (450 mm in width, 500 mm in length, and 38 µm in thickness) to which the mold release treatment was given were prepared on one surface. After apply|coating the varnish of the active energy ray hardening type adhesive to the surface to which the mold release process was given of the polyethylene terephthalate film of 1 sheet using the applicator, it dried at 80 degreeC for 5 minutes, and the adhesive layer was formed. Next, the surface to which the release treatment of one polyethylene terephthalate film was given and the pressure-sensitive adhesive layer were bonded together at room temperature and pressed with a rubber roll to form a polyethylene terephthalate film, an adhesive layer having a thickness of 30 µm, and a polyethylene terephthalate film. A laminate was obtained. A plurality of such laminates were produced. Next, one side of the polyethylene terephthalate film of the laminate is peeled off, and the adhesive layers are laminated so that voids do not enter each other, and this is done using another laminate until the thickness of the adhesive layer is about 1 mm. By repeating laminating an adhesive layer, the laminated body which consists of two polyethylene terephthalate films and the adhesive layer of about 1 mm in thickness sandwiched between these was obtained.

The obtained laminated body was punched out to 10 mm (phi), the polyethylene terephthalate film was peeled on both sides, and it arrange|positioned on the slide glass so that a void might not enter. Next, the aluminum foil whose single side is black was similarly punched out by 10 mm (phi), and the sample was obtained by arrange|positioning on the upper surface of the adhesive layer on the opposite side to the slide glass. The obtained sample was irradiated with ultraviolet rays under the same conditions as [Preparation of dicing and die-bonding integrated film], and using a resin curing shrinkage measuring device (Acro Edge Co., Ltd., Custron), slide glasses before and after irradiation with ultraviolet rays And curing shrinkage was measured from the difference in thickness excluding the aluminum foil. A result is shown in Table 2.

(4) Measurement of the edge peel strength of the chip

Edge peeling strength is measured through the following process. Fig.9 (a), Fig.9 (b), and Fig.9(c) are sectional drawing which shows typically the process of measuring edge peeling strength.

· A step of attaching a silicon wafer Ws with a thickness of 50 μm to the adhesive layer 5 and attaching a dicing ring DR to the second surface F2 of the pressure-sensitive adhesive layer 3 (FIG. 9(a) ) Reference)

· A step of separating the silicon wafer Ws and the adhesive layer 5 into a plurality of chips Ta with adhesive pieces (a laminate of the chips Ts and the adhesive pieces 5p) (see Fig. 9(b)) )

· At a temperature of 23°C, the central portion of the chip with an adhesive piece Ta from the side of the base material layer 1 is press-fitted at a speed of 60 mm/min (see FIG. 9(c) ), and the edge of the chip with an adhesive piece Ta is an adhesive Process of measuring edge peel strength when peeled from layer (3)

First, a dicing die-bonding integrated film was affixed to a silicon wafer (diameter: 12 inches, thickness: 50 µm) and a dicing ring under the following conditions (refer to Fig. 9(a)). The elongation in the MD direction of the dicing die-bonding integrated film after affixing the silicon wafer and the dicing ring was about 1.0 to 1.3%.

<Attachment Conditions>

・Attaching device: DFM2800 (manufactured by Disco Co., Ltd.)

・Attaching temperature: 70℃

・Attaching speed: 10mm/s

・Attachment tension level: Level 6

Next, the dicing die-bonding integrated film affixed silicon wafer was divided into a plurality of chips with adhesive pieces (size 2 mm x 2 mm) by blade dicing (refer to Fig. 9(b)).

<Dicing conditions>

・Dicer: DFD6361 (manufactured by Disco Co., Ltd.)

・Blade: ZH05-SD4000-N1-70-BB (manufactured by Disco Co., Ltd.)

・Blade rotation speed: 40000rpm

Dicing speed: 30mm/sec

·Blade height: 90μm

· Notch depth from the surface of the pressure-sensitive adhesive layer to the substrate layer: 20 μm

・Quantity at the time of dicing

Blade cooler: 1.5L/min

Shower: 1.0L/min

Spray: 1.0L/min

One day after dicing, the chip with the adhesive piece was press-fitted from the base layer side with the press-fitting jig P under the following measurement conditions, and the edge peel strength of the chip with the adhesive piece was measured (FIG. 9(c)). Reference). Fig. 10 is a graph showing an example of the relationship between the displacement (mm) due to press fit and the press force (N). When the edge of the chip peels, as shown in FIG. 10, the pressing force temporarily decreases, and a change point occurs in the graph. The value of the pressing force at this change point is defined as edge peeling strength. In addition, before the measurement, the surface of the base material layer corresponded to the center part of a chip|tip was marked with an oil-based pen. Fig. 11 is a plan view schematically showing a state in which a mark is attached at a position corresponding to the central portion of a chip to be measured. The mark M at the center of the chip was determined by measuring with a ruler. The measurement was performed with N=10. After measurement for one chip, the next measurement was performed with an interval equal to three chips (see Fig. 11). A result is shown in Table 2.

<Measurement conditions>

・Measuring device: EZ-SX compact tabletop tester (manufactured by Shimadzu Corporation)

· Load cell: 50N

・Pressure-fitting jig: Attachment attached to the ZTS series (shape: conical, manufactured by Imada Co., Ltd.)

·Indentation speed: 60mm/min

・Temperature: 23℃

Humidity: 45±10%

(5) Evaluation of pick-up properties

After the measurement of said edge peeling strength, 100 chips|tips with an adhesive bond piece were picked up on condition of the following.

<Pick-up conditions>

・Die bonder device: DB800-HSD (manufactured by Hitachi High-Technologies Co., Ltd.)

Push-up pin: EJECTOR NEEDLE SEN2-83-05 (diameter: 0.7 mm, tip shape: hemisphere with a radius of 350 μm, manufactured by Micro Mechanics)

·Push-up height: 200μm

・Push-up speed: 1mm/sec

In addition, one push-up pin was arrange|positioned at the center part of a chip|tip. The pick-up success rate was 100% "A", what was 70% or more and less than 100% was "B", and what was less than 70% was made into "C". A result is shown in Table 2.

[Table 2]

As shown in Table 2, the dicing and die-bonding integrated films of Examples 1 to 5 had better pickup properties than the dicing and die-bonding integrated films of Comparative Example 1. Specifically, in Comparative Example 1, the difference in (f2-f1) was larger than in Examples 1 to 5, so the cure shrinkage rate and edge peel strength were also higher than in Examples 1 to 5, and the pickup properties were not sufficient. From the above results, the dicing and die-bonding integrated film of the present disclosure can be applied to a semiconductor device manufacturing process including a step of segmenting a wafer into a plurality of small chips (area 0.1 to 9 mm ² ), and excellent pick-up property It was confirmed that the adhesive layer which has

One… base layer
3… adhesive layer
3a… first area
3b… second area
5… adhesive layer
5P, 5P… adhesive piece
5C… cured product
8… DAF
10… Dicing and die-bonding integrated film (film)
42… pin
44… suction collet
50… sealing layer
60… struct
70… Board
80… support plate
100… semiconductor device
DR… dicing ring
F1… side 1
F2… 2nd side
M… Mark
P… press fit jig
Rw… area
S1, S2, S3, S4, S, Ts... chip
Ta… Chip with adhesive piece
W… wafer
Ws… silicon wafer
W1, W2, W3, W4… wire

Claims (12)

a base layer,
A pressure-sensitive adhesive layer made of an active energy ray-curable pressure-sensitive adhesive having a first surface facing the base layer and a second surface opposite to the first surface;
and an adhesive layer provided to cover the central portion of the second surface,
The pressure-sensitive adhesive layer has a first region including at least a region corresponding to the wafer affixing position in the adhesive layer, and a second region positioned to surround the first region,
The first region is a region in a state in which adhesive force is lowered compared to that of the second region by irradiation of active energy rays,
The adhesive force of the first region of the pressure-sensitive adhesive layer to the adhesive layer, measured under the conditions of a peeling angle of 30° and a peeling rate of 60 mm/min at a temperature of 23°C, is f1 (N/25mm), peeling at a temperature of 23°C The difference between f2 and f1 (f2-f1) when the adhesive force of the second region of the pressure-sensitive adhesive layer to the adhesive layer measured under the conditions of an angle of 30° and a peeling rate of 60 mm/min is f2 (N/25 mm) ) is 6.5~9.0N/25mm,
A dicing and die-bonding integrated film applied to a manufacturing process of a semiconductor device including a step of segmenting a wafer into a plurality of chips having an area of 0.1 to 9 mm ² . The method according to claim 1,
The difference between f2 and f1 (f2-f1) is 7.0 to 9.0 N/25 mm, a dicing and die-bonding integrated film. The method according to claim 1 or 2,
Said f1 is 1.1-4.5N/25mm, The dicing die-bonding integrated film. 4. The method according to any one of claims 1 to 3,
The said f1 is 1.1-3.0N/25mm, The dicing die-bonding integrated film. 5. The method according to any one of claims 1 to 4,
The adhesive force of the second region of the pressure-sensitive adhesive layer to the stainless substrate, measured under the conditions of a peeling angle of 90° and a peeling rate of 50 mm/min at a temperature of 23° C., is 0.2 N/25 mm or more, a dicing die-bonding integrated film . 6. The method according to any one of claims 1 to 5,
The active energy ray-curable pressure-sensitive adhesive includes 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,
Content of the said functional group in the said (meth)acrylic-type resin is 0.1-1.2 mmol/g, The dicing die-bonding integrated film. 7. The method of claim 6,
The active energy ray-curable pressure-sensitive adhesive further comprises a crosslinking agent,
The content of the said crosslinking agent with respect to the total mass of the said active energy ray-curable adhesive is 0.1-15 mass %, The dicing die-bonding integrated film. 8. The method of claim 7,
The dicing and die-bonding integrated film, wherein the crosslinking 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 hydroxyl groups in one molecule. 9. The method according to any one of claims 1 to 8,
The irradiation amount of the said active energy ray is 10-1000mJ/cm< ² > The dicing die-bonding integrated film. 10. The method according to any one of claims 1 to 9,
The dicing and die-bonding integrated film, wherein the adhesive layer comprises an adhesive composition containing a reactive group-containing (meth)acrylic copolymer, a curing accelerator, and a filler. As a manufacturing method of the dicing die-bonding integrated film in any one of Claims 1-10,
A step of producing a laminate comprising a pressure-sensitive adhesive layer made of an active energy ray-curable pressure-sensitive adhesive on the surface of the base layer, and the adhesive layer formed on the surface of the pressure-sensitive adhesive layer;
A method for producing a dicing and die-bonding integrated film comprising the step of irradiating an active energy ray to a region serving as the first region of the pressure-sensitive adhesive layer included in the laminate in this order. A step of preparing the dicing and 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 and die-bonding integrated film and attaching a dicing ring to the second surface of the pressure-sensitive adhesive layer;
dividing the wafer into a plurality of chips;
a step of picking up the chip from the pressure-sensitive adhesive layer together with an adhesive piece in which the adhesive layer is separated into pieces;
and mounting the chip on a substrate or another chip via the adhesive piece.

Images