JP7471880B2 - Film-like adhesive and dicing die bonding sheet - Google Patents

Description

The present invention relates to a film-like adhesive and a dicing die bonding sheet.

The semiconductor chip is usually die-bonded to the circuit formation surface of the substrate using a film-like adhesive (sometimes called a "die-bonding film") provided on the backside of the semiconductor chip. Then, if necessary, one or more semiconductor chips are stacked on top of this semiconductor chip, wire bonding is performed, and the whole result is sealed with resin to produce a semiconductor package. This semiconductor package is then used to produce the desired semiconductor device.

A semiconductor chip having a film-like adhesive on the back surface is produced, for example, by dividing a semiconductor wafer having a film-like adhesive on the back surface and cutting the film-like adhesive. As a method for dividing a semiconductor wafer into semiconductor chips in this way, for example, a method of dicing the semiconductor wafer together with the film-like adhesive using a dicing blade is widely used. In this case, the film-like adhesive before cutting is used as a dicing die bonding sheet that is laminated and integrated with a support sheet (sometimes called a "dicing sheet") used to fix the semiconductor wafer during dicing.
After dicing, the semiconductor chips having the film-like adhesive on their rear surfaces (semiconductor chips with film-like adhesive) are separated from the support sheet and picked up.

When picking up the semiconductor chip, it is necessary that the film adhesive can be easily separated from the support sheet together with the semiconductor chip. For example, if the adhesive strength of the film adhesive to the support sheet is too strong, it becomes difficult to pick up the semiconductor chip with the film adhesive attached, and the film adhesive peels off from the semiconductor chip and remains on the support sheet. If such film adhesive frequently remains, it not only causes process problems but also increases the manufacturing costs of the semiconductor device.

In response to this, a dicing/die bonding integrated tape (corresponding to the dicing/die bonding sheet) has been disclosed (see Patent Document 1) that is made up of a base layer, an adhesive layer, and an adhesive layer (corresponding to the film-like adhesive) laminated in that order, and the breaking elongation of the adhesive layer is adjusted to a specific range before and after irradiation with electron beams, ultraviolet rays, or visible light. It is said that by using this dicing/die bonding integrated tape, semiconductor chips with film-like adhesive can be picked up satisfactorily even if the force applied to the semiconductor chip during pick-up is reduced.

JP 2015-126217 A

However, the dicing die bonding sheet (integrated dicing and die bonding tape) described in Reference 1 requires the use of a support sheet equipped with an adhesive layer for direct contact with the film adhesive in order to improve the pick-up suitability of the semiconductor chip with the film adhesive, which limits the options for the support sheet.

The present invention aims to provide a film-like adhesive that can be laminated with a support sheet to form a dicing die bonding sheet, and that can suppress the film-like adhesive from remaining on the support sheet when picking up a semiconductor chip with the film-like adhesive, without requiring a support sheet with a pressure-sensitive adhesive layer for direct contact with the film-like adhesive, and a dicing die bonding sheet equipped with the film-like adhesive.

The present invention relates to a curable film-like adhesive, which is a laminate of a plurality of the film-like adhesive sheets, and a first test piece having a thickness of 200 μm is subjected to a tear test by a right-angle tear method in accordance with JIS K7128-3, with the distance between a pair of gripping tools gripping and fixing the first test piece being 60 mm, and the tear speed being 200 mm/min. When the amount of displacement in the tear direction of the first test piece when the tear strength of the first test piece exhibits a maximum value _Tmax is defined as _D1 , and the tear strength when the amount of displacement is _0.6D1 is defined as _T1 , the following formula can be obtained:
ΔT=(T ₁ /0.6)−T _max
The present invention provides a film-like adhesive having an absolute value of ΔT calculated by the following formula:
The film-like adhesive of the present invention comprises a cured product of the film-like adhesive having a size of 2 mm x 2 mm and a thickness of 20 μm, a copper plate having a thickness of 500 μm provided over the entire surface of one side of the cured product, and a silicon chip having a thickness of 350 μm provided over the entire surface of the other side of the cured product, and when a second test piece is prepared in which the side of the cured product and the side of the silicon chip are aligned, and with the copper plate fixed, a force is applied to the aligned portions of the side of the cured product and the side of the silicon chip in the second test piece at a speed of 200 μm/sec in a direction parallel to one side of the cured product at the same time, it is preferable that the maximum value of the force applied until the cured product is destroyed, the cured product is peeled off from the copper plate, or the cured product is peeled off from the silicon chip is 100 N/2 mm□ or more.
In the film-like adhesive of the present invention, when the tear test is conducted, it is preferable that the displacement in the tear direction of the first test piece from when the tear strength of the first test piece reaches its maximum until the first test piece breaks is 15 mm or less.

The present invention provides a dicing die bonding sheet comprising a support sheet and a film adhesive provided on one side of the support sheet, the film adhesive being the film adhesive of the present invention described above.
In the dicing/die bonding sheet of the present invention, it is preferable that the support sheet consists of only a base material.

According to the present invention, a film-like adhesive that can be laminated with a support sheet to form a dicing die bonding sheet and that can suppress the film-like adhesive from remaining on the support sheet when picking up a semiconductor chip with the film-like adhesive, without requiring a support sheet with a pressure-sensitive adhesive layer for direct contact with the film-like adhesive, and a dicing die bonding sheet equipped with the film-like adhesive are provided.

FIG. 2 is a plan view showing a first test piece produced using a film adhesive according to one embodiment of the present invention. FIG. 2 is a cross-sectional view for illustrating a method for measuring the adhesive strength of a cured product of a film-like adhesive according to one embodiment of the present invention. FIG. 1 is a cross-sectional view illustrating a schematic example of a film-like adhesive according to one embodiment of the present invention. 1 is a cross-sectional view showing a schematic example of a dicing die bonding sheet according to one embodiment of the present invention. 1 is a cross-sectional view showing a schematic diagram of another example of a dicing-die bonding sheet according to one embodiment of the present invention. FIG. 1A to 1C are cross-sectional views for illustrating a schematic example of a method for manufacturing a semiconductor device when a dicing die bonding sheet according to one embodiment of the present invention is used. 1A to 1C are cross-sectional views for illustrating a schematic example of a method for manufacturing a semiconductor device when a film adhesive according to an embodiment of the present invention is used.

Film-like adhesive The film-like adhesive according to one embodiment of the present invention is a curable film-like adhesive, and is a laminate of a plurality of the film-like adhesive. A tear test is carried out on a first test piece having a thickness of 200 μm in accordance with JIS K7128-3, with the distance between a pair of gripping tools gripping and fixing the first test piece being 60 mm, and a tear speed being 200 mm/min, by a right-angle tear method. When the tear strength of the first test piece exhibits a maximum value _Tmax , the displacement amount in the tear direction of the first test piece is defined as _D1 , and when the tear strength when the displacement amount is _0.6D1 is defined as _T1 , the following formula:
ΔT=(T ₁ /0.6)−T _max
The absolute value of ΔT calculated by is 10 N/mm or less.

The film-like adhesive of this embodiment can be laminated with a support sheet or a dicing sheet to form a dicing die bonding sheet.
Furthermore, because the film adhesive of the present embodiment has such tearing properties, it is possible to prevent the film adhesive from remaining on the support sheet or dicing sheet when picking up the semiconductor chip with the film adhesive, even without using a support sheet or dicing sheet equipped with a pressure-sensitive adhesive layer for direct contact with the film adhesive. This makes it possible to prevent the occurrence of process troubles and reduce the manufacturing costs of semiconductor devices.

The film-like adhesive of this embodiment has curing properties and may be either thermosetting or energy ray curing, or may have both thermosetting and energy ray curing properties. When the film-like adhesive has both thermosetting and energy ray curing properties, if the contribution of heat curing to the curing is greater than the contribution of energy ray curing, the film-like adhesive is treated as being thermosetting. Conversely, if the contribution of energy ray curing to the curing is greater than the contribution of heat curing, the film-like adhesive is treated as being energy ray curing. For example, when the film-like adhesive is cured by heating the film-like adhesive without irradiating it with energy rays, the film-like adhesive is treated as being thermosetting.

In this specification, the term "energy rays" refers to electromagnetic waves or charged particle beams that have an energy quantum. Examples of energy rays include ultraviolet rays, radiation, and electron beams. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED lamp as an ultraviolet ray source. Electron beams can be irradiated by generating them using an electron beam accelerator or the like.
In this specification, "energy ray curable" means a property that is cured by irradiation with energy rays, and "non-energy ray curable" means a property that is not cured even when irradiated with energy rays.

When the film-like adhesive has thermosetting properties, it is preferable that the film-like adhesive has pressure-sensitive adhesive properties. A film-like adhesive having both thermosetting properties and pressure-sensitive adhesive properties can be applied to various adherends by lightly pressing it when uncured. The film-like adhesive may also be one that can be applied to various adherends by heating and softening it. The film-like adhesive eventually becomes a cured product with high impact resistance when cured, and this cured product can retain sufficient adhesive properties even under harsh conditions of high temperature and high humidity.

When the cured product of the film-like adhesive is actually used, the curing conditions for curing the film-like adhesive to form a cured product are not particularly limited as long as the degree of curing of the cured product is sufficiently high, and may be appropriately selected depending on the type of film-like adhesive.
The heating temperature during thermal curing of the thermosetting film-like adhesive is preferably 100 to 200° C., and may be, for example, any one of 125 to 185° C. and 150 to 170° C. The heating time during thermal curing is preferably 0.5 to 5 hours, and may be, for example, any one of 0.5 to 4 hours and 0.5 to 3 hours.
The illuminance of the energy rays during energy ray curing of the energy ray-curable film-like adhesive is preferably 60 to 320 mW/cm ^2. The amount of energy rays during the energy ray curing is preferably 100 to 1000 mJ/cm ² .

<<ΔT>>
When the film-like adhesive of this embodiment has a ΔT (N/mm) within a specific range as described below, the above-described effect of suppressing the film-like adhesive from remaining on the support sheet is enhanced.
The first test piece, which is the subject of calculation of ΔT, can be prepared, for example, by using a plurality of film-like adhesives of the present embodiment, each having a thickness of less than 200 μm, laminating these to produce a laminated sheet having a total thickness of 200 μm, and then cutting this laminated sheet into a specified shape and size so that the tear strength can be measured in accordance with JIS K7128-3.
A plan view of the first test piece together with its size is shown in Fig. 1. In the first test piece 99 in Fig. 1, the unit of the numerical value indicating the length is "mm".

The ΔT can be calculated by the following method.
That is, a tear test was performed on the first test piece by a right-angle tear method in accordance with JIS K7128-3, with the distance between a pair of gripping tools gripping and fixing the first test piece being 60 mm, the tear speed being 200 mm/min, and the displacement amount in the tear direction of the first test piece when the tear strength of the first test piece exhibits a maximum value _Tmax is defined as _D1 , and the tear strength when the displacement amount is _0.6D1 is defined as _T1 . The following formula was obtained:
ΔT=(T ₁ /0.6)−T _max
It is calculated as follows.

The thicknesses of the multiple sheets of film-like adhesive that make up the first test piece and the laminated sheet may all be the same, may all be different, or may only be partially the same. However, in terms of making it easier to prepare the first test piece and the laminated sheet, it is preferable that the thicknesses of the multiple sheets of film-like adhesive are all the same.

The number of sheets of the film-like adhesive constituting the first test piece and the laminate sheet is not particularly limited as long as it is two or more sheets, and can be selected arbitrarily depending on the thickness of each film-like adhesive.
For example, when the thickness of the multiple sheets of film-like adhesive is the same, taking into consideration the fact that it is easier to prepare one sheet of film-like adhesive, the first test piece and the laminated sheet can be prepared more easily by using 10 sheets of film-like adhesive having a thickness of 20 μm. However, this is only one example, and the number and thickness of the film-like adhesives used are not limited to this.

The "right-angle tear method" performed on the first test piece is "Test method for tear strength of plastic films and sheets, Part 3: right-angle tear method" specified in JIS K7128-3.
When the first test piece is gripped and fixed with gripping tools, the distance between the pair of gripping tools is 60 mm, which means that when a tear test is performed, the length of the stretchable portion of the first test piece in the tear direction of the first test piece is 60 mm before the tear test is performed, and this length is the length of the portion of the first test piece that is subject to the tear test.

The TD plane is considered by taking the tear strength T of the first test piece as one coordinate axis (vertical axis) and the displacement D in the tear direction of the first test piece as the other coordinate axis (horizontal axis) perpendicular to the one coordinate axis.
In the above formula, "T ₁ /0.6" represents a straight line that passes through the origin (0,0) and the two points of coordinates (0.6D ₁ ,T ₁ ) on the TD plane:
T = ( _T1 / _0.6D1 )D
In this case, D= _D1 is the value of T.
A curve is obtained by plotting T and D of the first test piece on the T-D plane. When this curve has a convex shape in the direction in which T increases, the following formula is satisfied:
T1 _/ 0.6> _Tmax
That is, the relationship (T ₁ /0.6)-T _max >0 is established. Conversely, when the shape is convex in the direction in which T decreases, the following formula is satisfied:
T1/ _{0.6 <Tmax}
That is, the relationship (T ₁ /0.6)−T _max <0 holds.
In the film-like adhesive of this embodiment, regardless of the shape of the curve, the difference between "T ₁ /0.6" and "T _max " is 10 N/mm or less, i.e., the absolute value of ΔT (|ΔT|) is 10 N/mm or less (-10 N/mm≦ΔT≦10 N/mm). By satisfying this condition, the above-mentioned effect of suppressing the remaining of the film-like adhesive on the support sheet is high.

|ΔT| may be, for example, 7 N/mm or less, 5 N/mm or less, or 3 N/mm or less, at which point the above-mentioned effect is further enhanced.

The lower limit of |ΔT| is not particularly limited. For example, the film-like adhesive having |ΔT| of 1 N/mm or more can be manufactured more easily.

|ΔT| may be any value within a range that is set by any combination of the above-mentioned lower limit value and any of the upper limit values. For example, in one embodiment, |ΔT| is preferably 1 to 10 N/mm or less, and may be, for example, any of 1 to 7 N/mm, 1 to 5 N/mm, and 1 to 3 N/mm. However, these are just examples of |ΔT|.

|ΔT| can be adjusted by adjusting the type or amount of the components contained in the film-like adhesive. For example, |ΔT| can be adjusted over a wide range by adjusting the type or amount of the components in the film-like adhesive that are solid at room temperature, the crosslinking agent, etc. In the case of a thermosetting film-like adhesive, |ΔT| can be adjusted over a wide range by adjusting the type or amount of the polymer component (a), the epoxy resin (b1) that is solid at room temperature, the crosslinking agent (f), etc., which will be described later.

In this specification, "room temperature" means a temperature that is neither particularly cold nor hot, i.e., a normal temperature, such as a temperature between 15 and 25°C.

<<Adhesive strength of the cured film adhesive>>
The semiconductor chip with the film-like adhesive produced using the film-like adhesive of this embodiment is attached (die-bonded) to the circuit formation surface of the substrate by the film-like adhesive therein. Furthermore, the film-like adhesive is finally cured by irradiation with energy rays.
Therefore, the cured product of the film-like adhesive is required to have sufficient adhesive strength to the object to be adhered.

The degree of adhesive strength of the cured product of the film-like adhesive can be determined, for example, by preparing a second test piece comprising a cured product of the film-like adhesive having a size of 2 mm x 2 mm and a thickness of 20 μm, a copper plate having a thickness of 500 μm provided on the entire surface of one side of the cured product, and a silicon chip having a thickness of 350 μm provided on the entire surface of the other side of the cured product, with the side of the cured product and the side of the silicon chip aligned, and applying a force at a speed of 200 μm/sec in a direction parallel to one side of the cured product at the same time to the aligned portions of the side of the cured product and the side of the silicon chip in the second test piece with the copper plate fixed, using as an index the maximum value of the force (i.e., adhesive strength) applied until the cured product is destroyed, the cured product is peeled off from the copper plate, or the cured product is peeled off from the silicon chip.
In the second test piece, the cured product and the silicon chip may be the same size except for the thickness, and further, all sides of the cured product and the silicon chip may be aligned with each other. Such a second test piece is easy to prepare, as described later in the Examples.

FIG. 2 is a cross-sectional view for illustrating a method for measuring the adhesive strength of the cured product of the film-like adhesive.
In addition, the figures used in the following explanation may show key parts enlarged for convenience in order to make the features of the present invention easier to understand, and the dimensional ratios of each component may not necessarily be the same as the actual ones.
In addition, in FIG. 2 and subsequent figures, the same components as those shown in the figures already described are given the same reference numerals as in the figures already described, and detailed description thereof will be omitted.

When measuring the adhesive strength, a second test piece 9 is prepared.
The second test piece 9 is composed of a cured product 90 of a film-like adhesive, a copper plate 91 provided on the entire surface of one side 90b of the cured product 90 (sometimes referred to as the "second side" in this specification), and a silicon chip 92 provided on the entire surface of the other side 90a of the cured product 90 (sometimes referred to as the "first side" in this specification).

The cured film-like adhesive 90 is a cured film-like adhesive of this embodiment.
The first surface 90a and the second surface 90b of the cured body 90 each have a rectangular (square) planar shape.
The size of the cured product 90 (the size of the first surface 90a and the second surface 90b) is 2 mm×2 mm, and the thickness of the cured product 90 is 20 μm.

The copper plate 91 is 500 μm thick, and the silicon chip 92 is 350 μm thick.

In the second test piece 9, the side 90c of the cured film-like adhesive 90 and the side 92c of the silicon chip 92 are aligned; for example, in this cross section, in the direction parallel to the first surface 90a or the second surface 90b of the film-like adhesive 90, the position of the side 90c of the film-like adhesive 90 and the position of the side 92c of the silicon chip 92 coincide with each other.

It is preferable that at least the portion of the side surface 92c of the silicon chip 92 that is aligned with the side surface 90c of the cured film-like adhesive 90 be flat.
The size of the contact surface of the silicon chip 92 with the cured product 90 may be equal to or larger than the size of the first surface 90 a of the cured product 90 .
The planar shape of the surface of the silicon chip 92 that comes into contact with the cured product 90 is preferably rectangular, and may be, for example, square, and is preferably the same as the planar shape of the first surface 90 a of the cured product 90 .
As described later in the examples, when forming the cured product 90 by cutting and curing a film-like adhesive (not shown), and forming silicon chips 92 by dividing a silicon wafer (not shown), a process can be adopted in which these cutting and dividing steps are carried out continuously. In this case, the contact surface of the silicon chip 92 with the cured product 90 and the first surface 90a of the cured product 90 can be made the same size and shape, and further, the side surface 90c of the cured product 90 and the side surface 92c of the silicon chip 92 can be easily aligned.

The size of the contact surface of the copper plate 91 with the cured product 90 of the film-like adhesive may be equal to or larger than the size of the second surface 90b of the cured product 90, and is preferably larger.
The planar shape of the copper plate 91's contact surface with the cured material 90 is not particularly limited as long as the copper plate 91 can cover the entire second surface 90b of the cured material 90, and may be, for example, rectangular.

When measuring the adhesive strength, with the copper plate 91 fixed, a force P is simultaneously applied to the aligned portions of the side surface 90c of the cured product 90 of the film-like adhesive in the second test piece 9 and the side surface 92c of the silicon chip 92 in a direction parallel to one surface (the first surface 90a or the second surface 90b) of the cured product 90 at a speed of 200 μm/sec. Here, a case is shown in which the force P is applied to the above-mentioned aligned portions using a pressing means 8.
In order to measure the adhesive strength with higher accuracy, the portion where the pressing means 8 applies the force is preferably flat, and the pressing means 8 is more preferably plate-shaped.
The pressing means 8 may be made of, for example, metal.

As described above, when applying force P to the cured film adhesive 90 and the silicon chip 92 simultaneously, it is preferable not to bring the pressing means 8 into contact with the copper plate 91.

In this embodiment, force P is applied to the aligned portion between the side 90c of the cured film adhesive 90 and the side 92c of the silicon chip 92, and the maximum value of force P applied until the cured film 90 is destroyed, peeled off from the copper plate 91, or peeled off from the silicon chip 92 is used as the adhesive strength of the cured film 90.

The adhesive strength of the cured film-like adhesive is preferably 100 N/2 mm□ or more, more preferably 110 N/2 mm□ or more, and may be, for example, 125 N/2 mm□ or more, 140 N/2 mm□ or more, or 170 N/2 mm□ or more.

The upper limit of the adhesive strength is not particularly limited. For example, the film-like adhesive having an adhesive strength of 300 N/2 mm□ or less can be manufactured more easily.

The adhesive strength may be any value within a range that is set by any combination of any of the lower limit values and upper limit values described above. For example, in one embodiment, the adhesive strength is preferably 100 to 300 N/2 mm□, more preferably 110 to 300 N/2 mm□, and may be, for example, any of 125 to 300 N/2 mm□, 140 to 300 N/2 mm□, and 170 to 300 N/2 mm□. However, these are just examples of the adhesive strength.

In this embodiment, the cured product of the film-like adhesive in the second test piece that defines the adhesive strength is a thermoset product obtained by heat-treating a thermosetting film-like adhesive at 160°C for 1 hour. The cured product also includes a cured product of a film-like adhesive that has both thermosetting and energy ray curing properties. Such a cured product also includes, for example, a thermoset product obtained by irradiating an energy ray to a film-like adhesive before heat curing, and then further heating the semi-cured product at 160°C for 1 hour.

In this specification, the unit "N/2mm□" is synonymous with "N/(2mm x 2mm)."

The adhesive strength can be adjusted by adjusting the type or amount of the components contained in the film-like adhesive. For example, the adhesive strength can be adjusted over a wide range by adjusting the type or amount of the polymer component, curable component, filler, coupling agent, etc. contained in the film-like adhesive. In the case of a thermosetting film-like adhesive, the adhesive strength can be adjusted over a wide range by adjusting the type or amount of the polymer component (a), thermosetting component (b), filler (d), coupling agent (e), etc. described below.

<_<D0>>
In the film-like adhesive of this embodiment, when a tear test is performed in accordance with JIS K7128-3 on a first test piece which is a laminate of a plurality of sheets of the film-like adhesive and has a thickness of 200 μm, with the distance between a pair of grippers gripping and fixing the first test piece being 60 mm and the tear speed being 200 mm/min, using a right-angle tear method, it is preferable that the displacement in the tear direction of the first test piece from when the tear strength of the first test piece reaches a maximum until the first test piece breaks (sometimes referred to as "D ₀ " in this specification) is 15 mm or less. By having such tear characteristics, the film-like adhesive of this embodiment has a higher effect of suppressing the remaining of the film-like adhesive on the support sheet described above.

The first test piece used in measuring _D0 is the same as the first test piece used in calculating ΔT described above, and the tear test performed in measuring _D0 is the same as the tear test performed in calculating ΔT described above. That is, the measurement of _D0 and the calculation of ΔT can be performed simultaneously.

When the tear test was performed, the first test piece was elongated in the tear direction, and the tear strength of the first test piece increased with the elongation. After the tear strength of the first test piece reached a maximum, the first test piece was further elongated, and at some stage, the first test piece broke.
The displacement in the tear direction of the first test piece when the tear test was conducted is a numerical value obtained by subtracting the distance between the grips at any time during the tear test from the distance between the grips at any time prior to that time, and corresponds to the difference in length of the first test piece in the tear direction of the first test piece at these different times. And _D0 is a numerical value (Sb - Sm) obtained by subtracting the distance between the grips _Sm when the tear strength of the first test piece reaches its maximum from the _distance between the grips _Sb when the first test piece breaks after the tear strength of the first test piece reaches its _maximum .

In the film-like adhesive of this embodiment, _D0 is preferably 170 mm or less, and may be, for example, any one of 15 mm or less, 14.5 mm or less, 13 mm or less, and 10 mm or less. By having _D0 be equal to or less than the upper limit, the effect of suppressing the remaining of the film-like adhesive on the support sheet described above is further enhanced.

There is no particular limitation on the lower limit of D _0. For example, the film-like adhesive having a D ₀ of 5 mm or more can be produced more easily.

_D0 may be any value within a range that is set by arbitrarily combining the above-mentioned lower limit value and any of the upper limit values. For example, in one embodiment, _D0 is preferably 5 to 170 mm, and may be, for example, any of 5 to 15 mm, 5 to 14.5 mm, 5 to 13 mm, and 5 to 10 mm. However, these are just examples of _D0 .

D0 can be adjusted by adjusting the type or amount of the components contained in the film-like adhesive. For example, _D0 can be adjusted within a wide range by adjusting the type or amount of the components in the film-like adhesive that are solid at room temperature, the crosslinking agent, etc. In the case of a thermosetting film-like adhesive, _D0 can be adjusted within a wide _range by adjusting the type or amount of the polymer component (a), the epoxy resin (b1) that is solid at room temperature, the crosslinking agent (f), etc., which will be described later.

FIG. 3 is a cross-sectional view illustrating an example of a film-like adhesive according to this embodiment.
The film-like adhesive 13 shown here has a first release film 151 on one side (sometimes referred to in this specification as the "first side") 13a, and a second release film 152 on the other side (sometimes referred to in this specification as the "second side") 13b opposite the first side 13a.
Such a film-like adhesive 13 is suitable for storage, for example, in a roll form.

The |ΔT| of a first test piece prepared using the film-like adhesive 13 or a film-like adhesive having the same composition as the film-like adhesive 13 is 10 N/mm or less.
The adhesive strength of the cured product in a second test piece prepared using the film-like adhesive 13 or a film-like adhesive having the same composition as the film-like adhesive 13 is preferably 100 N/2 mm□ or more.
The D ₀ of a first test piece prepared using the film-like adhesive 13 or a film-like adhesive having the same composition as the film-like adhesive 13 _is preferably 15 mm or less.

The first release film 151 and the second release film 152 may both be of known types.
The first release film 151 and the second release film 152 may be the same as each other, or may be different from each other, for example, in that the peeling force required to peel them from the film-like adhesive 13 is different from each other.

In the film-like adhesive 13 shown in FIG. 1, the first release film 151 and the second release film 152 are both removed, and one of the resulting exposed surfaces becomes the surface to be attached to the semiconductor wafer, and the other becomes the surface to be attached to the substrate (adhesive surface). For example, when the first surface 13a is the surface to be attached to the semiconductor wafer, the second surface 13b becomes the surface to be attached to the substrate.

In FIG. 1, an example is shown in which the release film is provided on both sides (first side 13a, second side 13b) of the film-like adhesive 13, but the release film may be provided on only one side of the film-like adhesive 13, i.e., only the first side 13a or only the second side 13b.

The film-like adhesive of this embodiment may consist of one layer (single layer), or may consist of two or more layers. When it consists of multiple layers, these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited.

In this specification, not limited to the case of a film-like adhesive, "multiple layers may be the same or different" means "all layers may be the same, all layers may be different, or only some layers may be the same," and further, "multiple layers are different" means "at least one of the constituent materials and thicknesses of each layer is different from each other."

The thickness of the film-like adhesive is not particularly limited, but is preferably 2 to 100 μm, more preferably 2 to 70 μm, and may be, for example, 2 to 40 μm. When the thickness of the film-like adhesive is equal to or greater than the lower limit, the adhesive strength of the film-like adhesive is higher. When the thickness of the film-like adhesive is equal to or less than the upper limit, the manufacturing suitability of the film-like adhesive is higher, for example, the suitability of applying the adhesive composition described below in a required thickness is higher.
Here, "thickness of the film adhesive" means the thickness of the entire film adhesive; for example, the thickness of a film adhesive consisting of multiple layers means the total thickness of all layers that make up the film adhesive.

The film-like adhesive can be formed using an adhesive composition containing its constituent materials. For example, the adhesive composition can be applied to a surface on which the film-like adhesive is to be formed, and dried as necessary to form the film-like adhesive at a desired location. The thermosetting film-like adhesive can be formed using a thermosetting adhesive composition, and the energy ray-curable film-like adhesive can be formed using an energy ray-curable adhesive composition.
The ratio of the contents of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the contents of the components in the film-like adhesive.

The adhesive composition may be applied by a known method, such as a method using various coaters, such as an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Mayer bar coater, or kiss coater.

The drying conditions for the adhesive composition are not particularly limited, but when the adhesive composition contains a solvent described below, it is preferable to heat-dry the adhesive composition. The adhesive composition containing a solvent is preferably dried, for example, at 70 to 130° C. for 10 seconds to 5 minutes.
The components of the film-like adhesive and the adhesive composition will be described in detail below.

<<Thermosetting adhesive composition>>
The thermosetting adhesive composition may, for example, contain a polymer component (a) and a thermosetting component (b) (sometimes abbreviated as "composition (III-1)" in this specification). Each component will be described below.

<Polymer component (a)>
The polymer component (a) is a polymer compound for imparting film-forming properties, flexibility, etc. to the film-like adhesive. The polymer component (a) has thermoplastic properties and does not have thermosetting properties. In this specification, the polymer compound also includes products of polycondensation reactions.

The polymer component (a) contained in the composition (III-1) and the film-like adhesive may be one type or two or more types. When there are two or more types, the combination and ratio of the two or more types can be selected arbitrarily.

Examples of the polymer component (a) include acrylic resins, urethane resins, phenoxy resins, silicone resins, and saturated polyester resins.
Of these, the polymer component (a) is preferably an acrylic resin.

The acrylic resin in the polymer component (a) may be any known acrylic polymer.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000, and may be, for example, 500,000 to 1,000,000. When the weight average molecular weight of the acrylic resin is within such a range, it becomes easy to adjust the adhesive strength between the film-like adhesive and the adherend to a preferred range.
On the other hand, when the weight average molecular weight of the acrylic resin is equal to or greater than the lower limit, the shape stability (stability over time during storage) of the film-like adhesive is improved. Also, when the weight average molecular weight of the acrylic resin is equal to or less than the upper limit, the film-like adhesive is more likely to conform to the uneven surface of the adherend, and the occurrence of voids between the adherend and the film-like adhesive is further suppressed.

In this specification, unless otherwise specified, "weight average molecular weight" refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70°C, more preferably -45 to 50°C, and may be, for example, -35 to 30°C. When the Tg of the acrylic resin is equal to or greater than the lower limit, the adhesive strength between the film-like adhesive and the adherend is suppressed, making it easier to separate the semiconductor chip with the film-like adhesive from the support sheet (described below) when picked up. When the Tg of the acrylic resin is equal to or less than the upper limit, the adhesive strength between the film-like adhesive and the semiconductor chip is improved.

When an acrylic resin has two or more structural units, the glass transition temperature (Tg) of the acrylic resin can be calculated using the Fox formula. The Tg of the monomer from which the structural unit is derived can be the value listed in the Polymer Data Handbook or the Adhesive Handbook.

Examples of the (meth)acrylic acid ester constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, and p) (meth)acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms, such as isononyl acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (stearyl (meth)acrylate);
(meth)acrylic acid cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate;
(Meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate;
(Meth)acrylic acid cycloalkenyl esters such as (meth)acrylic acid dicyclopentenyl ester;
(Meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicyclopentenyloxyethyl ester;
(Meth)acrylic acid imide;
glycidyl group-containing (meth)acrylic acid esters such as glycidyl (meth)acrylate;
hydroxyl group-containing (meth)acrylic acid esters such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate;
Examples of such esters include (meth)acrylic acid esters containing a substituted amino group, such as N-methylaminoethyl (meth)acrylate. Here, the term "substituted amino group" refers to a group having a structure in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.

In this specification, the term "(meth)acrylic acid" is intended to encompass both "acrylic acid" and "methacrylic acid." The same applies to terms similar to (meth)acrylic acid.

The acrylic resin may be, for example, a resin obtained by copolymerizing one or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc., in addition to the (meth)acrylic acid ester.

The acrylic resin may be made up of one type of monomer or two or more types of monomers, and when two or more types are used, the combination and ratio of these monomers can be selected arbitrarily.

In addition to the above-mentioned hydroxyl groups, the acrylic resin may have functional groups capable of bonding with other compounds, such as vinyl groups, (meth)acryloyl groups, amino groups, carboxy groups, and isocyanate groups. These functional groups, including the hydroxyl groups of the acrylic resin, may be bonded to other compounds via a crosslinking agent (f) described below, or may be bonded directly to other compounds without the crosslinking agent (f). When the acrylic resin bonds to other compounds via the functional groups, the cohesive strength of the film-like adhesive is improved, and the physical stability of the film-like adhesive is improved.

In the present invention, as the polymer component (a), a thermoplastic resin other than an acrylic resin (hereinafter sometimes simply abbreviated as "thermoplastic resin") may be used alone without using an acrylic resin, or may be used in combination with an acrylic resin. By using the thermoplastic resin, the semiconductor chip with the film-like adhesive can be more easily detached from the support sheet described below during pick-up, and the film-like adhesive can more easily follow the uneven surface of the adherend, which can further suppress the occurrence of voids between the adherend and the film-like adhesive.

The weight average molecular weight of the thermoplastic resin is preferably 1,000 to 100,000, and more preferably 3,000 to 80,000.

The glass transition temperature (Tg) of the thermoplastic resin is preferably -30 to 150°C, and more preferably -20 to 120°C.

Examples of the thermoplastic resin include polyester resin, urethane resin, phenoxy resin, polybutene, polybutadiene, polystyrene, etc.

The thermoplastic resin contained in composition (III-1) and the film-like adhesive may be one type or two or more types, and when there are two or more types, the combination and ratio of the resins can be selected arbitrarily.

In composition (III-1), the ratio of the content of polymer component (a) to the total content of all components other than the solvent (i.e., the ratio of the content of polymer component (a) to the total mass of the film-like adhesive in the film-like adhesive) is preferably 5 to 40 mass%, more preferably 6 to 30 mass%, and may be, for example, 7 to 25 mass%, regardless of the type of polymer component (a). This makes the structure of the film-like adhesive more stable. By having this ratio be equal to or less than the upper limit, the balance between the effect of using polymer component (a) and the effect of using components other than polymer component (a) can be adjusted in a wide range.

In composition (III-1) and the film-like adhesive, the ratio of the acrylic resin content to the total content of polymer component (a) is preferably 25 to 100% by mass, and may be, for example, any of 50 to 100% by mass, 70 to 100% by mass, and 90 to 100% by mass. When the content ratio is equal to or greater than the lower limit, the storage stability of the film-like adhesive is improved.

By adjusting the weight average molecular weight of the polymer component (a) and the content of the polymer component (a) in the film-like adhesive, _D0 and |ΔT| can be more easily adjusted. For example, by using a polymer component (a) with a large weight average molecular weight, or by increasing the content of the polymer component (a) with a large weight average molecular weight in the film-like adhesive, _D0 and |ΔT| can be more easily reduced.

<Thermosetting component (b)>
The thermosetting component (b) has thermosetting properties and is a component for thermally curing the film-like adhesive.
The thermosetting component (b) contained in the adhesive composition and the film-like adhesive may be one type or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

Examples of the thermosetting component (b) include epoxy-based thermosetting resins, polyimide resins, and unsaturated polyester resins.
Among these, the thermosetting component (b) is preferably an epoxy-based thermosetting resin.

Epoxy Thermosetting Resin The epoxy thermosetting resin is composed of an epoxy resin (b1) and a thermosetting agent (b2).
The adhesive composition and the film-like adhesive may contain only one type of epoxy thermosetting resin, or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[Epoxy resin (b1)]
Examples of the epoxy resin (b1) include known epoxy resins, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, orthocresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenylene skeleton type epoxy resins, and other epoxy compounds having two or more functionalities.

The epoxy resin (b1) may be an epoxy resin having an unsaturated hydrocarbon group. An epoxy resin having an unsaturated hydrocarbon group has a higher compatibility with acrylic resin than an epoxy resin not having an unsaturated hydrocarbon group. Therefore, by using an epoxy resin (b1) having an unsaturated hydrocarbon group, the reliability of the package obtained using the film-like adhesive is improved.

Epoxy resins having unsaturated hydrocarbon groups include, for example, compounds having a structure in which some of the epoxy groups of a multifunctional epoxy resin are converted to groups having unsaturated hydrocarbon groups. Such compounds can be obtained, for example, by subjecting the epoxy groups to an addition reaction with (meth)acrylic acid or a derivative thereof.

In this specification, unless otherwise specified, the term "derivative" refers to a compound having a structure in which one or more groups of the original compound are replaced with other groups (substituents). Here, the term "group" includes not only an atomic group formed by bonding multiple atoms, but also a single atom.

Furthermore, examples of epoxy resins having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), a (meth)acryloyl group, and a (meth)acrylamide group, with an acryloyl group being preferred.

The number average molecular weight of the epoxy resin (b1) is not particularly limited, but from the viewpoints of the curability of the film-like adhesive and the strength and heat resistance of the cured film-like adhesive, it is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000.
The epoxy equivalent of the epoxy resin (b1) is preferably 100 to 1000 g/eq., and may be, for example, any one of 150 to 650 g/eq, 150 to 300 g/eq, or any one of 450 to 1000 g/eq, and 700 to 1000 g/eq.

By selecting an epoxy resin (b1) that is solid at room temperature and adjusting the content in the film-like adhesive, it is possible to more easily adjust |ΔT| and D _0. For example, by increasing the content in the film-like adhesive of the epoxy resin (b1) that is solid at room temperature, it is possible to more easily reduce |ΔT| and D ₀ .

The epoxy resin (b1) contained in the composition (III-1) and the film-like adhesive may be one type or two or more types. When there are two or more types, the combination and ratio of the two or more types can be selected arbitrarily.

[Thermal curing agent (b2)]
The thermosetting agent (b2) is a curing agent for the epoxy resin (b1).
The thermosetting agent (b2) may be, for example, a compound having two or more functional groups capable of reacting with an epoxy group in one molecule. The functional group may, for example, be a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, or an anhydride group of an acid group, and is preferably a phenolic hydroxyl group, an amino group, or an anhydride group of an acid group, and more preferably a phenolic hydroxyl group or an amino group.

Among the heat curing agents (b2), examples of phenolic curing agents having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins.
Among the heat curing agents (b2), examples of amine-based curing agents having an amino group include dicyandiamide (DICY) and the like.

The heat curing agent (b2) may have an unsaturated hydrocarbon group.
Examples of the heat curing agent (b2) having an unsaturated hydrocarbon group include a compound in which some of the hydroxyl groups of a phenol resin are substituted with a group having an unsaturated hydrocarbon group, and a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring of a phenol resin.
The unsaturated hydrocarbon group in the heat curing agent (b2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

When a phenol-based hardener is used as the heat-curing agent (b2), it is preferable that the heat-curing agent (b2) has a high softening point or glass transition temperature, since this makes it easier to adjust the adhesive strength of the film-like adhesive.

Of the thermosetting agents (b2), for example, the number average molecular weight of resin components such as polyfunctional phenol resins, novolac-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000.
Of the thermosetting agents (b2), the molecular weight of the non-resin components, such as biphenol and dicyandiamide, is not particularly limited, but is preferably, for example, 60 to 500.

The composition (III-1) and the film-like adhesive may contain only one type of heat curing agent (b2), or two or more types. When two or more types are contained, the combination and ratio of the two or more types can be selected arbitrarily.

In the composition (III-1) and the film-like adhesive, the content of the heat curing agent (b2) is preferably 1 to 60 parts by mass relative to 100 parts by mass of the epoxy resin (b1), and may be, for example, 1 to 35 parts by mass, 1 to 10 parts by mass, or 20 to 60 parts by mass, or 40 to 60 parts by mass. When the content of the heat curing agent (b2) is equal to or greater than the lower limit, the curing of the film-like adhesive proceeds more easily. When the content of the heat curing agent (b2) is equal to or less than the upper limit, the moisture absorption rate of the film-like adhesive is reduced, and the reliability of the package obtained using the film-like adhesive is improved.

In the composition (III-1) and the film-like adhesive, the content of the thermosetting component (b) (for example, the total content of the epoxy resin (b1) and the thermosetting agent (b2)) is preferably 20 to 1000 parts by mass, more preferably 20 to 700 parts by mass, relative to 100 parts by mass of the content of the polymer component (a), and may be, for example, any of 50 to 600 parts by mass, 100 to 600 parts by mass, and 200 to 600 parts by mass. When the content of the thermosetting component (b) is in such a range, it becomes easier to adjust the adhesive strength between the film-like adhesive and the support sheet described later. In addition, when the content of the thermosetting component (b) is in such a range, |ΔT| and D ₀ can be more easily adjusted.

In order to improve various physical properties of the film-like adhesive, the composition (III-1) and the film-like adhesive may contain, in addition to the polymer component (a) and the thermosetting component (b), other components not falling within the above categories, as necessary.
Examples of other components contained in the composition (III-1) and the film-like adhesive include a curing accelerator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), an energy ray-curable resin (g), a photopolymerization initiator (h), a colorant (i), and a general-purpose additive (j).

<Curing Accelerator (c)>
The curing accelerator (c) is a component for adjusting the curing rate of the composition (III-1) and the film-like adhesive.
Preferred examples of the curing accelerator (c) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are substituted with groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (phosphines in which one or more hydrogen atoms are substituted with organic groups); tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, and other tetraphenylboron salts; and inclusion compounds in which the imidazoles are used as guest compounds.

The curing accelerator (c) contained in the composition (III-1) and the film-like adhesive may be one type or two or more types. When there are two or more types, the combination and ratio of the two or more types can be selected arbitrarily.

When the curing accelerator (c) is used, the content of the curing accelerator (c) in the composition (III-1) and the film-like adhesive is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the thermosetting component (b). When the content of the curing accelerator (c) is equal to or greater than the lower limit, the effect of using the curing accelerator (c) is more pronounced. When the content of the curing accelerator (c) is equal to or less than the upper limit, for example, the effect of suppressing the highly polar curing accelerator (c) from migrating to the adhesive interface with the adherend and segregating in the film-like adhesive under high temperature and high humidity conditions is enhanced, and the reliability of the package obtained using the film-like adhesive is further improved.

<Filler (d)>
By containing the filler (d), the thermal expansion coefficient of the film adhesive can be easily adjusted, and by optimizing this thermal expansion coefficient for the object to which the film adhesive is attached, the reliability of the package obtained using the film adhesive is further improved. Furthermore, by containing the filler (d) in the film adhesive, it is also possible to reduce the moisture absorption rate of the cured product of the film adhesive and improve the heat dissipation properties.

The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, and the like; beads obtained by spheronizing these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, and the like.
Among these, the inorganic filler is preferably silica, alumina or a surface-modified product thereof.

The average particle diameter of the filler (d) is not particularly limited, but is preferably 10 nm to 5 μm, and may be, for example, any of 10 to 800 nm, 10 to 600 nm, 20 to 300 nm, and 30 to 150 nm. When the average particle diameter of the filler (d) is in such a range, the effect of using the filler (d) can be fully obtained, and the storage stability of the film-like adhesive is improved.

In this specification, unless otherwise specified, the term "average particle size" refers to the particle size (D ₅₀ ) value at an integrated value of 50% in a particle size distribution curve determined by a laser diffraction scattering method.

The composition (III-1) and the film-like adhesive may contain only one type of filler (d), or two or more types. When two or more types are contained, the combination and ratio of the fillers can be selected arbitrarily.

When filler (d) is used, the ratio of the content of filler (d) to the total content of all components other than the solvent in composition (III-1) (i.e., the ratio of the content of filler (d) to the total mass of the film-like adhesive in the film-like adhesive) is preferably 5 to 60 mass%, more preferably 10 to 45 mass%, and may be, for example, 10 to 20 mass%. When the content of filler (d) is in such a range, it becomes easier to adjust the thermal expansion coefficient.

<Coupling Agent (e)>
The film-like adhesive contains a coupling agent (e) to improve its adhesiveness and adhesion to the adherend. In addition, the film-like adhesive contains a coupling agent (e) to improve the water resistance of the cured product without impairing its heat resistance. The coupling agent (e) has a functional group capable of reacting with an inorganic compound or an organic compound.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional groups of the polymer component (a), the thermosetting component (b), etc., and is more preferably a silane coupling agent.
Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, and 3-(2-aminoethylamino)propyltrimethoxysilane. Examples of the organosiloxane include phenylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane, and oligomeric or polymeric organosiloxane.

The coupling agent (e) contained in the composition (III-1) and the film-like adhesive may be one type or two or more types. When two or more types are contained, the combination and ratio of the coupling agents can be selected arbitrarily.

When a coupling agent (e) is used, the content of the coupling agent (e) in the composition (III-1) and the film-like adhesive is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (b). When the content of the coupling agent (e) is equal to or greater than the lower limit, the effects of using the coupling agent (e), such as improved dispersibility of the filler (d) in the resin and improved adhesion of the film-like adhesive to the adherend, are more significantly obtained. When the content of the coupling agent (e) is equal to or less than the upper limit, the generation of outgassing is further suppressed.

<Crosslinking Agent (f)>
When the polymer component (a) is one having a functional group capable of bonding with other compounds, such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxyl group, or an isocyanate group, such as the above-mentioned acrylic resin, the composition (III-1) and the film-like adhesive may contain a crosslinking agent (f) for bonding the functional group with other compounds to effect crosslinking. By crosslinking with the crosslinking agent (f), the initial adhesive strength and cohesive strength of the film-like adhesive can be adjusted.
Furthermore, by using the crosslinking agent (f), |ΔT| and D ₀ can be more easily adjusted.

Examples of the crosslinking agent (f) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridinyl group), etc.

Examples of the organic polyisocyanate compound include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyisocyanate compounds, etc."); trimers, isocyanurates, and adducts of the aromatic polyisocyanate compounds; and terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyisocyanate compounds, etc. with polyol compounds. The "adduct" refers to a reaction product of the aromatic polyisocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyisocyanate compound with a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil. Examples of the adduct include a tolylene diisocyanate trimer adduct of trimethylolpropane, as described below. Also, "terminal isocyanate urethane prepolymer" refers to a prepolymer that has a urethane bond and an isocyanate group at the end of the molecule.

Specific examples of the organic polyisocyanate compound include 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; a compound in which one or more of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate are added to all or some of the hydroxyl groups of a polyol such as trimethylolpropane; lysine diisocyanate, etc.

Examples of the organic polyvalent imine compounds include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinyl propionate, tetramethylolmethane-tri-β-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide)triethylenemelamine, etc.

When an organic polyisocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the polymer component (a). When the crosslinking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, a crosslinked structure can be easily introduced into the film-like adhesive by the reaction between the crosslinking agent (f) and the polymer component (a).

The crosslinking agent (f) contained in the composition (III-1) and the film-like adhesive may be one type or two or more types. When there are two or more types, the combination and ratio of the crosslinking agents can be selected arbitrarily.

When the crosslinking agent (f) is used, the content of the crosslinking agent (f) in the adhesive composition is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the polymer component (a). When the content of the crosslinking agent (f) is equal to or greater than the lower limit, the effect of using the crosslinking agent (f) is more pronounced. When the content of the crosslinking agent (f) is equal to or less than the upper limit, excessive use of the crosslinking agent (f) is suppressed. In addition, when the content of the crosslinking agent (f) is within such a range, |ΔT| and D ₀ can be more easily adjusted. For example, by increasing the content of the crosslinking agent (f), |ΔT| and D ₀ can be more easily reduced.

When the crosslinking agent (f) is not used, i.e., when the content of the crosslinking agent (f) is 0 parts by mass, there is no need to wait for the crosslinking reaction caused by the action of the crosslinking agent (f) to be completed after the film-like adhesive is formed, which is advantageous in that the process time can be shortened.

<Energy Ray Curable Resin (g)>
The film-like adhesive contains the energy ray-curable resin (g) and thus the properties thereof can be changed by irradiation with energy rays.

The energy ray curable resin (g) is obtained from an energy ray curable compound.
Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth)acryloyl group are preferred.

Examples of the acrylate compounds include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and the like. Examples of such (meth)acrylates include (meth)acrylates containing a chain aliphatic skeleton such as dicyclopentanyl di(meth)acrylate; (meth)acrylates containing a cyclic aliphatic skeleton such as dicyclopentanyl di(meth)acrylate; polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylate; oligoester (meth)acrylates; urethane (meth)acrylate oligomers; epoxy-modified (meth)acrylates; polyether (meth)acrylates other than the above-mentioned polyalkylene glycol (meth)acrylates; and itaconic acid oligomers.

The weight average molecular weight of the energy ray curable resin (g) is preferably 100 to 30,000, and more preferably 300 to 10,000.

The energy ray curable resin (g) contained in the composition (III-1) may be one type or two or more types. When two or more types are contained, the combination and ratio of the resins may be selected arbitrarily.

When an energy ray curable resin (g) is used, the content of the energy ray curable resin (g) in the composition (III-1) relative to the total mass of the composition (III-1) is preferably 1 to 95 mass%, and may be, for example, any one of 1 to 50 mass%, 1 to 25 mass%, and 1 to 10 mass%.

<Photopolymerization initiator (h)>
When the composition (III-1) and the film-like adhesive contain an energy ray-curable resin (g), they may contain a photopolymerization initiator (h) in order to efficiently proceed with the polymerization reaction of the energy ray-curable resin (g).

Examples of the photopolymerization initiator (h) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2,2-dimethoxy-1,2-diphenylethane-1-one; and acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Examples of the compounds include aryl ether compounds; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; and quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.
Examples of the photopolymerization initiator (h) include photosensitizers such as amines.

The photopolymerization initiator (h) contained in the composition (III-1) and the film-like adhesive may be one type or two or more types. When two or more types are contained, the combination and ratio of the photopolymerization initiators may be selected arbitrarily.

When a photopolymerization initiator (h) is used, the content of the photopolymerization initiator (h) in the composition (III-1) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass, per 100 parts by mass of the energy ray-curable resin (g).

<Colorant (i)>
The colorant (i) is a component that can adjust the transmittance of light of various wavelengths in the film-like adhesive and its cured product.
Examples of the colorant (i) include known colorants such as inorganic pigments, organic pigments, and organic dyes.

Examples of the organic pigments and organic dyes include aminium-based dyes, cyanine-based dyes, merocyanine-based dyes, croconium-based dyes, squalium-based dyes, azulenium-based dyes, polymethine-based dyes, naphthoquinone-based dyes, pyrylium-based dyes, phthalocyanine-based dyes, naphthalocyanine-based dyes, naphtholactam-based dyes, azo-based dyes, condensed azo-based dyes, indigo-based dyes, perinone-based dyes, perylene-based dyes, dioxazine-based dyes, quinacridone-based dyes, isoindolinone-based dyes, quinophthalone-based dyes, pyrrole-based dyes, thioindigo-based dyes, metal complex-based dyes (metal complex dyes), dithiol metal complex-based dyes, indolephenol-based dyes, triarylmethane-based dyes, anthraquinone-based dyes, dioxazine-based dyes, naphthol-based dyes, azomethine-based dyes, benzimidazolone-based dyes, pyranthrone-based dyes, and threne-based dyes.

Examples of the inorganic pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO (indium tin oxide)-based pigments, and ATO (antimony tin oxide)-based pigments.

The colorant (i) contained in the composition (III-1) and the film-like adhesive may be one type or two or more types. When there are two or more types, the combination and ratio of the colorants can be selected arbitrarily.

When colorant (i) is used, the content of colorant (i) in composition (III-1) and the film-like adhesive can be adjusted as appropriate depending on, for example, the type of colorant (i). Usually, in composition (III-1), the ratio of the content of colorant (i) to the total content of all components other than the solvent (i.e., the ratio of the content of colorant (i) in the film-like adhesive to the total mass of the film-like adhesive) is preferably 0.01 to 10 mass%, regardless of the type of colorant (i). When the ratio is equal to or greater than the lower limit, the effect of using colorant (i) is more pronounced. When the ratio is equal to or less than the upper limit, excessive use of colorant (i) is suppressed.

<General-purpose additives (j)>
The general-purpose additive (j) may be a known one and may be selected arbitrarily according to the purpose, and is not particularly limited. Preferable general-purpose additives (j) include, for example, plasticizers, antistatic agents, antioxidants, gettering agents, antifoaming agents, leveling agents, etc.

The general-purpose additive (i) contained in the composition (III-1) and the film-like adhesive may be one type or two or more types. When there are two or more types, the combination and ratio thereof can be selected arbitrarily.
The content of the general-purpose additive (i) in the composition (III-1) and the film-like adhesive is not particularly limited and can be appropriately selected depending on, for example, the type of the general-purpose additive (i).

<Solvent>
The composition (III-1) preferably further contains a solvent, since the composition (III-1) containing a solvent has good handleability.
The solvent is not particularly limited, but preferred examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The composition (III-1) may contain only one type of solvent, or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

The solvent contained in composition (III-1) is preferably methyl ethyl ketone or the like, since this allows the components contained in composition (III-1) to be mixed more uniformly.

The content of the solvent in composition (III-1) is not particularly limited and may be selected appropriately depending on, for example, the types of components other than the solvent.

<<Energy ray curable adhesive composition>>
Examples of the energy ray-curable adhesive composition include those containing an energy ray-curable component (sometimes abbreviated as "composition (III-2)" in this specification). For example, the energy ray-curable adhesive composition may contain an energy ray-curable component, a polymer having no energy ray-curable group, and a photopolymerization initiator.

Examples of the energy ray-curable component include a resin having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group) such as an acryloyl group, and a group capable of reacting with other compounds, such as a glycidyl group.
The epoxy resin (b1) in the composition (III-1) described above contains one that corresponds to the energy ray-curable component.

Examples of the polymer having no energy ray-curable group include an acrylic resin, a phenoxy resin, a urethane resin, a polyester resin, a rubber-based resin, and an acrylic urethane resin.
Among these, the polymer having no energy ray-curable group is preferably an acrylic resin.
Among the polymer components (a) in the above-described (III-1), there are those that correspond to the polymers that do not have the energy ray-curable group.

The photopolymerization initiator may be, for example, the same as the photopolymerization initiator (h) in the composition (III-1) described above.

The contents of the energy ray curable component, the polymer not having an energy ray curable group, and the photopolymerization initiator in composition (III-2) may be appropriately adjusted according to the types of these components, and are not particularly limited. For example, if any of the energy ray curable component, the polymer not having an energy ray curable group, and the photopolymerization initiator corresponds to any of the components contained in composition (III-1), the content of that component in composition (III-2) can be the same as the content of the corresponding component in composition (III-1).

Depending on the purpose, the composition (III-2) may contain other components that do not fall under any of the energy ray-curable component, the polymer not having an energy ray-curable group, and the photopolymerization initiator.
Examples of the other components include one or more selected from the group consisting of epoxy resins, thermosetting agents, fillers, coupling agents, crosslinking agents, colorants, general-purpose additives, and solvents.

The epoxy resin, heat curing agent, filler, coupling agent, crosslinking agent, colorant, general-purpose additive, and solvent in composition (III-2) are the same as the epoxy resin (b1), heat curing agent (b2), filler (d), coupling agent (e), crosslinking agent (f), colorant (i), general-purpose additive (j), and solvent in composition (III-1).

The contents of the epoxy resin, heat curing agent, filler, coupling agent, crosslinking agent, colorant, general-purpose additive, and solvent in composition (III-2) may be appropriately adjusted according to the purpose, and are not particularly limited.

<<Method of manufacturing adhesive composition>>
The adhesive composition (thermosetting adhesive composition, energy ray-curable adhesive composition) can be obtained by blending the respective components constituting the adhesive composition.
The order of addition of the components is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, the solvent may be used by mixing it with any of the other ingredients to pre-dilute the ingredients, or the solvent may be used by mixing it with any of the other ingredients without pre-diluting the ingredients.

The method for mixing the components during blending is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or stirring blade, a method of mixing using a mixer, a method of mixing by applying ultrasound, etc.
The temperature and time during addition and mixing of each component are not particularly limited as long as the components do not deteriorate, and may be adjusted appropriately. The temperature is preferably 15 to 30°C.

◇Dicing die bonding sheet A dicing die bonding sheet according to one embodiment of the present invention comprises a support sheet and a film-like adhesive provided on one side of the support sheet, the film-like adhesive being the film-like adhesive according to one embodiment of the present invention described above.
The dicing die bonding sheet of the present embodiment can be used as a sheet for producing the above-described semiconductor chips with a film-like adhesive by dividing a semiconductor wafer into semiconductor chips by dicing, for example. That is, the support sheet in the dicing die bonding sheet can be used as a dicing sheet.

<<Support sheet>>
The support sheet may be one layer (single layer) or two or more layers. When the support sheet is made of multiple layers, the constituent materials and thicknesses of the multiple layers may be the same or different from each other, and the combination of the multiple layers is not particularly limited as long as it does not impair the effects of the present invention.

Examples of the support sheet include those consisting of only a substrate; those comprising a substrate and an adhesive layer provided on one side of the substrate; and those comprising a substrate and a functional layer other than the adhesive layer provided on one side of the substrate.

When the support sheet has the substrate and the adhesive layer, in the dicing die bonding sheet, the adhesive layer is disposed between the substrate and the film-like adhesive.

When the support sheet comprises the substrate and a functional layer, in the dicing die bonding sheet, the functional layer may be arranged on the film-like adhesive side of the substrate, or on the side opposite the film-like adhesive side of the substrate.
In this embodiment, the functional layer disposed on the film-like adhesive side of the substrate is referred to as the "intermediate layer", and the functional layer disposed on the opposite side of the substrate to the film-like adhesive side is referred to as the "back layer". The intermediate layer is disposed on the film-like adhesive side of the substrate, thereby imparting a new function other than adhesiveness to the support sheet or dicing die bonding sheet. The back layer is disposed on the opposite side of the substrate to the film-like adhesive side, thereby imparting a new function other than adhesiveness to the support sheet or dicing die bonding sheet. Examples of the back layer include an antistatic layer for preventing static electricity of the support sheet or dicing die bonding sheet; an anti-adhesion layer for preventing adhesion between support sheets or between dicing die bonding sheets, or adhesion of the support sheet or dicing die bonding sheet to the adsorption table when the support sheets or dicing die bonding sheets are stacked and stored.

The support sheet consisting of only the substrate is suitable not only as a dicing sheet but also as a carrier sheet. The dicing die bonding sheet having such a support sheet consisting of only the substrate is used by attaching the surface (i.e., the first surface) of the film adhesive opposite to the side having the support sheet (i.e., the substrate) to one surface of the semiconductor wafer.
When a support sheet consisting of only a base material is used, a dicing/die bonding sheet can be produced at low cost.

The support sheet having a base material and an adhesive layer, and the support sheet having a base material and a functional layer are suitable as a dicing sheet. The dicing die bonding sheet having such a support sheet is also used by attaching the surface (first surface) of the film adhesive opposite to the side having the support sheet to one surface of a semiconductor wafer.
When a support sheet having a substrate and an adhesive layer is used, the adhesive strength or adhesion between the support sheet and the film-like adhesive in the dicing die bonding sheet can be easily adjusted.
When a support sheet having a substrate and a functional layer is used, the support sheet or dicing die bonding sheet exhibits functions other than adhesiveness according to the properties of the functional layer.

Because the dicing die bonding sheet of this embodiment is provided with the film-like adhesive, even if the support sheet does not have a pressure-sensitive adhesive layer that is in direct contact with the film-like adhesive, when a semiconductor chip with a film-like adhesive is produced using the dicing die bonding sheet and then picked up, the remaining film-like adhesive on the support sheet can be suppressed.
In other words, the effects of the present invention are most pronounced when a dicing die bonding sheet having a configuration in which the adhesive layer and the film-like adhesive are not in direct contact, such as a dicing die bonding sheet in which a film-like adhesive is provided on a support sheet consisting only of a substrate, or a dicing die bonding sheet having a substrate and the functional layer, is used.

However, the dicing die bonding sheet of this embodiment may also have an adhesive layer that is in direct contact with the film-like adhesive. In that case, the action of the film-like adhesive and the action of the adhesive layer can more easily prevent the film-like adhesive from remaining on the support sheet when picking up the semiconductor chip with the film-like adhesive.

How to use the dicing die bonding sheet will be explained in detail later.
Each layer constituting the support sheet will now be described.

<Substrate>
The substrate is in the form of a sheet or film, and examples of the constituent materials thereof include various resins.
Examples of the resin include polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; ethylene-based copolymers (copolymers obtained using ethylene as a monomer) such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and ethylene-norbornene copolymer; vinyl chloride-based resins (copolymers obtained using vinyl chloride as a monomer) such as polyvinyl chloride and vinyl chloride copolymers. Examples of the polyester include polyesters such as poly(ethylene terephthalate), poly(ethylene naphthalate), poly(butylene terephthalate), polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and wholly aromatic polyesters in which all structural units have aromatic cyclic groups; copolymers of two or more of the above polyesters; poly(meth)acrylic acid esters; polyurethanes; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluororesins; polyacetals; modified polyphenylene oxides; polyphenylene sulfides; polysulfones; and polyether ketones.
Further, the resin may be, for example, a polymer alloy such as a mixture of the polyester and other resins. The polymer alloy of the polyester and other resins is preferably one in which the amount of the resin other than the polyester is relatively small.
Examples of the resin include crosslinked resins in which one or more of the resins exemplified above are crosslinked; and modified resins such as ionomers using one or more of the resins exemplified above.

Among these, the resin that is the constituent material of the substrate is preferably an olefin-based resin having a constituent unit derived from an olefin, such as polyethylene, polyolefins other than polyethylene, ethylene-based copolymers, etc. Among dicing die bonding sheets constituted by directly contacting the film-like adhesive with the substrate, dicing die bonding sheets in which the contact surface of the substrate with the film-like adhesive contains such a resin have a higher effect of suppressing the remaining of the film-like adhesive on the support sheet (in other words, the substrate) described above.
Moreover, the resin that is the constituent material of the substrate preferably does not have a polar group such as a carboxy group, a carbonyl group, a hydroxyl group, etc. A dicing die bonding sheet in which the contact surface of the substrate with the film-like adhesive contains such a resin also has a higher effect of suppressing the remaining of the film-like adhesive on the support sheet (in other words, the substrate) described above.

The resin constituting the base material may be one type only, or two or more types. If there are two or more types, the combination and ratio of these can be selected arbitrarily.

The substrate may be made of one layer (single layer) or may be made of two or more layers. When made of multiple layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.

The thickness of the substrate is preferably 50 to 300 μm, and more preferably 60 to 150 μm. By setting the thickness of the substrate within this range, the flexibility of the dicing die bonding sheet and its attachability to a semiconductor wafer are improved.
Here, the "thickness of the substrate" means the thickness of the entire substrate. For example, the thickness of a substrate consisting of multiple layers means the total thickness of all layers constituting the substrate.

In addition to the main constituent materials such as the resin, the substrate may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers).

The substrate may be transparent or opaque, may be colored according to the purpose, and may have other layers vapor-deposited thereon.

In order to improve adhesion to a layer (e.g., a pressure-sensitive adhesive layer, a film-like adhesive, etc.) provided thereon, the surface of the substrate may be subjected to a roughening treatment such as sandblasting or solvent treatment; or an oxidation treatment such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet light irradiation treatment, flame treatment, chromate treatment, or hot air treatment.
The surface of the substrate may be treated with a primer.
The substrate may have a release treatment layer on its surface, which can be formed by subjecting the substrate surface to a release treatment using any of various known release agents.
Furthermore, the substrate may have adhesiveness on at least one surface thereof by containing a specific range of components (for example, a resin, etc.).

When the support sheet is made of only the substrate, or when the support sheet has an exposed surface of the substrate, and the outermost layer on the film-like adhesive side of the support sheet is the substrate, it is preferable that the surface on the film-like adhesive side of the substrate (sometimes referred to as the "first surface" in this specification) has not been subjected to the above-mentioned oxidation treatment, primer treatment, or other surface treatment, in order to enhance the effect of suppressing the remaining of the film-like adhesive on the support sheet (in other words, the substrate) when picking up the semiconductor chip with the film-like adhesive.

The substrate can be manufactured by a known method. For example, a substrate containing a resin can be manufactured by molding a resin composition containing the resin.

<Adhesive Layer>
The pressure-sensitive adhesive layer is in the form of a sheet or film and contains a pressure-sensitive adhesive.
Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber-based resins, silicone resins, epoxy-based resins, polyvinyl ethers, polycarbonates, and polyester resins.

In this specification, "adhesive resin" includes both resins that are adhesive and resins that are adhesive. For example, the adhesive resins include not only resins that are adhesive themselves, but also resins that become adhesive when used in combination with other components such as additives, and resins that become adhesive in the presence of a trigger such as heat or water.

The adhesive layer may consist of one layer (single layer) or may consist of two or more layers. When it consists of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 100 μm, and may be, for example, any one of 1 to 60 μm and 1 to 30 μm.
Here, "the thickness of the adhesive layer" means the thickness of the entire adhesive layer, and for example, the thickness of an adhesive layer consisting of multiple layers means the total thickness of all layers that make up the adhesive layer.

The adhesive layer may be formed using an energy ray curable adhesive, or may be formed using a non-energy ray curable adhesive. That is, the adhesive layer may be either energy ray curable or non-energy ray curable. The physical properties of the energy ray curable adhesive layer before and after curing can be easily adjusted.

The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive composition can be applied to the surface on which the adhesive layer is to be formed, and then dried as necessary to form the adhesive layer at the desired location. The ratio of the contents of the components in the adhesive composition that do not vaporize at room temperature is usually the same as the ratio of the contents of the components in the adhesive layer.

The pressure sensitive adhesive composition can be applied in the same manner as the adhesive composition described above.

When the adhesive layer is energy ray curable, examples of the energy ray curable adhesive composition include an adhesive composition (I-1) containing a non-energy ray curable adhesive resin (I-1a) (hereinafter sometimes abbreviated as "adhesive resin (I-1a)") and an energy ray curable compound; an adhesive composition (I-2) containing an energy ray curable adhesive resin (I-2a) (hereinafter sometimes abbreviated as "adhesive resin (I-2a)") in which an unsaturated group has been introduced into the side chain of the adhesive resin (I-1a); and an adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray curable compound.

When the adhesive layer is non-energy ray curable, examples of the non-energy ray curable adhesive composition include adhesive composition (I-4) containing the adhesive resin (I-1a).

The adhesive compositions such as adhesive compositions (I-1) to (I-4) can be produced in the same manner as the adhesive compositions described above, except that the blending components are different.

<Functional layer>
The functional layer is in the form of a sheet or film, and preferably contains a resin.
The functional layer may be made of a resin, or may contain a resin and a component other than the resin.
The functional layer containing the resin can be formed, for example, by molding the resin or a composition for forming a functional layer containing the resin. The functional layer can also be formed by applying the composition for forming a functional layer to the surface on which the functional layer is to be formed and drying it as necessary.

The content of the resin in the composition for forming the functional layer is not particularly limited and can be, for example, 10 to 90% by mass, but this is just one example.

The functional layer may consist of one layer (single layer) or may consist of two or more layers. When it consists of multiple layers, these multiple layers may be the same or different from each other, and the combination of these functional layers is not particularly limited.

The thickness of the functional layer is not particularly limited and can be set appropriately depending on the type of the functional layer.
Here, "thickness of the functional layer" means the thickness of the entire functional layer; for example, the thickness of a functional layer consisting of multiple layers means the total thickness of all layers that make up the functional layer.

Next, an example of a dicing die bonding sheet of this embodiment will be described with reference to the drawings.

FIG. 4 is a cross-sectional view showing a schematic example of the dicing-die bonding sheet of the present embodiment.
The dicing die bonding sheet 101 shown here includes a support sheet 10 and a film-like adhesive 13 on one surface (first surface) 10a of the support sheet 10. The support sheet 10 is made of only a base material 11, and the dicing die bonding sheet 101, in other words, has a configuration in which the film-like adhesive 13 is laminated on one surface (sometimes referred to as the "first surface" in this specification) 11a of the base material 11. The dicing die bonding sheet 101 further includes a release film 15 on the film-like adhesive 13.

In the dicing die bonding sheet 101, a film-like adhesive 13 is laminated on the first surface 11a of the substrate 11, a jig adhesive layer 16 is laminated on a portion of the surface 13a of the film-like adhesive 13 opposite the side having the substrate 11 (sometimes referred to as the "first surface" in this specification), i.e., the area near the peripheral portion, and a release film 15 is laminated on the surface of the first surface 13a of the film-like adhesive 13 on which the jig adhesive layer 16 is not laminated, and on the surfaces 16a (top and side surfaces) of the jig adhesive layer 16 that are not in contact with the film-like adhesive 13.
The first surface 11 a of the substrate 11 is the same as the first surface 10 a of the support sheet 10 .

The film adhesive 13 is as described above.
The release film 15 is similar to the first release film 151 or the second release film 152 shown in FIG.

The jig adhesive layer 16 may be, for example, a single-layer structure containing an adhesive component, or a multi-layer structure in which layers containing an adhesive component are laminated on both sides of a core sheet.

With the release film 15 removed, the dicing die bonding sheet 101 is used by attaching the back surface of a semiconductor wafer (not shown) to the first surface 13a of the film-like adhesive 13, and further attaching the upper surface of the surface 16a of the jig adhesive layer 16 to a jig such as a ring frame.

FIG. 5 is a cross-sectional view showing a schematic diagram of another example of the dicing-die bonding sheet of the present embodiment.
The dicing die bonding sheet 102 shown here is the same as the dicing die bonding sheet 101 shown in Fig. 4 except that it does not include the jig adhesive layer 16. That is, in the dicing die bonding sheet 102, a film-like adhesive 13 is laminated on the first surface 11a of the base material 11 (the first surface 10a of the support sheet 10), and a release film 15 is laminated on the entire first surface 13a of the film-like adhesive 13.
In other words, the dicing die bonding sheet 102 is constructed by laminating the substrate 11, the film-like adhesive 13, and the release film 15 in this order in the thickness direction.

The dicing die bonding sheet 102 shown in FIG. 5 is used with the release film 15 removed, with the back surface of a semiconductor wafer (not shown) affixed to a portion of the central area of the first surface 13a of the film-like adhesive 13 in the width direction of the film-like adhesive 13, and further with an area near the periphery of the film-like adhesive 13 affixed to a jig such as a ring frame.

The dicing die bonding sheet of this embodiment is not limited to that shown in Figures 4 and 5, and may have some of the configurations shown in Figures 4 and 5 modified or removed, or may have other configurations added to those described above, within the scope that does not impair the effects of the present invention.

For example, the dicing die bonding sheet shown in Figures 4 and 5 may have other layers that do not fall into the category of a substrate, a film-like adhesive, or a release film provided at any location.
Examples of the other layers include the adhesive layer and functional layers (intermediate layer, back layer) described above. The adhesive layer is provided between the substrate 11 and the film-like adhesive 13. The intermediate layer of the functional layers is also provided between the substrate 11 and the film-like adhesive 13. The back layer of the functional layers is provided on the surface opposite to the first surface 11a of the substrate 11, and may be the outermost layer of the dicing die bonding sheet.

In the dicing/die bonding sheets shown in FIGS. 4 and 5, a gap may be formed between the release film and the layer in direct contact with this release film.
In the dicing/die bonding sheets shown in FIGS. 4 and 5, the size and shape of each layer can be adjusted as desired depending on the purpose.

Manufacturing method of the dicing die bonding sheet The dicing die bonding sheet can be manufactured by stacking the above-mentioned layers so that they are in a corresponding positional relationship, and adjusting the shape of some or all of the layers as necessary. The method of forming each layer is as described above.

For example, when a pressure-sensitive adhesive layer is laminated on a substrate during the production of a support sheet, the pressure-sensitive adhesive composition may be applied onto the substrate and dried as necessary.
Alternatively, the pressure-sensitive adhesive layer can be laminated on the substrate by coating the pressure-sensitive adhesive composition on a release film, drying it as necessary to form a pressure-sensitive adhesive layer on the release film, and then laminating the exposed surface of the pressure-sensitive adhesive layer to one surface of the substrate. In this case, the pressure-sensitive adhesive composition is preferably coated on the release-treated surface of the release film.
So far, the case where a pressure-sensitive adhesive layer is laminated on a substrate has been given as an example, but the above-mentioned method can also be applied to, for example, the case where other layers such as the functional layer described above are laminated on a substrate, or the case where the film-like adhesive is laminated on a substrate. When the film-like adhesive is laminated, the adhesive composition is used.

On the other hand, for example, when a new layer (hereinafter abbreviated as "second layer") is laminated on the top layer (hereinafter abbreviated as "first layer") already laminated on the substrate, the second layer is formed in advance on a release film using a composition for forming the second layer, and the exposed surface of the formed second layer opposite to the side in contact with the release film is bonded to the exposed surface of the first layer on the substrate, thereby forming a continuous two-layer laminate structure (in other words, a laminate structure of the first layer and the second layer). In this case, it is preferable that the composition is applied to the release-treated surface of the release film. The release film may be removed as necessary after the formation of the laminate structure. When the second layer is the film-like adhesive, the adhesive composition is used as the composition for forming the second layer.

In this way, all layers other than the base material that make up the dicing die bonding sheet can be formed in advance on a release film and laminated by laminating them onto the surface of the desired layer, so the dicing die bonding sheet can be manufactured by appropriately selecting the layers that will undergo this process as necessary.

The dicing die bonding sheet is usually stored with a release film attached to the surface of the outermost layer (e.g., a film-like adhesive) on the side opposite the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as the adhesive composition, is applied to this release film (preferably its release-treated surface) and dried as necessary to form a layer constituting the outermost layer on the release film, and the remaining layers are laminated by any of the methods described above on the exposed surface opposite the side in contact with the release film of this layer, and the release film is not removed and the layers are left in this laminated state, thereby obtaining a dicing die bonding sheet with a release film.

◇Semiconductor device manufacturing method (method of using dicing die bonding sheet)
<<Production method (1)>>
The dicing/die bonding sheet according to one embodiment of the present invention described above can be used when manufacturing a semiconductor device.
In this case, the manufacturing method of the semiconductor device may be, for example,
A lamination (1) process is performed by using the dicing die bonding sheet to prepare a laminate (1) having a semiconductor wafer and attached to a back surface of the semiconductor wafer by the film-like adhesive in the dicing die bonding sheet;
a dividing/cutting step of producing semiconductor chips by dividing the semiconductor wafers in the laminate (1), and cutting the film-like adhesive along the dividing points of the semiconductor wafers to produce a semiconductor chip assembly (1) with a film-like adhesive, in which a plurality of semiconductor chips with a film-like adhesive, each of which includes the semiconductor chip and the film-like adhesive after cutting provided on the back surface of the semiconductor chip, are held on the support sheet;
a pick-up (1) step of obtaining a semiconductor chip with a film-like adhesive by separating the semiconductor chip with the film-like adhesive in the semiconductor chip assembly with a film-like adhesive from the support sheet and picking it up;
and a die bonding step of die bonding the semiconductor chip in the obtained semiconductor chip with film-like adhesive to a circuit formation surface of a substrate using the film-like adhesive in the semiconductor chip with film-like adhesive (sometimes referred to in this specification as "manufacturing method (1)").
In the manufacturing method (1), a semiconductor device can be manufactured in the same manner as the conventional method, except that the dicing die bonding sheet according to one embodiment of the present invention described above is used instead of the conventional dicing die bonding sheet.

<Lamination (1) process>
In the lamination (1) step, for example, the surface of the film-like adhesive in the dicing die bonding sheet opposite the support sheet (i.e., the first surface) is attached to the back surface of a semiconductor wafer to produce a laminate (1).
This process can be carried out in the same manner as the conventional method of attaching a dicing die bonding sheet to the back surface of a semiconductor wafer, except that a dicing die bonding sheet according to one embodiment of the present invention described above is used instead of a conventional dicing die bonding sheet.

<Divide/Cut Process>
In the dividing/cutting step, the order of dividing the semiconductor wafers in the laminate (1) (production of semiconductor chips) and cutting the film-like adhesive in the laminate (1) is not particularly limited, and may be divided into the semiconductor wafers and cut into the film-like adhesive, or may be cut into the film-like adhesive and divided into the semiconductor wafers, or may be simultaneously divided into the semiconductor wafers and cut into the film-like adhesive. In addition, when dividing the semiconductor wafers and cutting the film-like adhesive are not simultaneously performed, dividing the semiconductor wafers and cutting the film-like adhesive may be performed continuously or stepwise.

The division of the semiconductor wafer and the cutting of the film-like adhesive can both be carried out by known methods.
For example, the semiconductor wafer can be divided and the film-like adhesive can be cut continuously by dicing such as blade dicing, laser dicing by irradiating a laser, or water dicing by spraying water containing an abrasive, etc. However, this is only one example of a method for dividing a semiconductor wafer and a method for cutting a film-like adhesive.

The film-like adhesive is cut along the division points of the semiconductor wafer, but in this case, if the film-like adhesive is cut after the semiconductor wafer is divided, the film-like adhesive is cut along the division points of the semiconductor wafer, i.e., the peripheral edge of the semiconductor chip. On the other hand, if the film-like adhesive is cut before the semiconductor wafer is divided, or if the film-like adhesive is cut at the same time as the semiconductor wafer is divided, the film-like adhesive is cut along the planned division points of the semiconductor wafer.

In the semiconductor chip assembly (1) with film-like adhesive produced in this process, multiple semiconductor chips with film-like adhesive are held (fixed) in an aligned state on the single support sheet that constituted the dicing die bonding sheet.

<Pickup (1) process>
In the pick-up (1) step, the semiconductor chips with the film-like adhesive in the semiconductor chip assembly with the film-like adhesive (1) can be picked up by detaching them from the support sheet using a known method.
In this process, by using the film-like adhesive (dicing die bonding sheet) according to one embodiment of the present invention described above, even if the support sheet does not have a pressure-sensitive adhesive layer for direct contact with the film-like adhesive, it is possible to suppress the film-like adhesive from remaining on the support sheet when picking up the semiconductor chip with the film-like adhesive.

<Die bonding process>
In the die bonding step, the semiconductor chip with the film-like adhesive after picking up can be die-bonded to the circuit formation surface of the substrate by the film-like adhesive therein, using a known method.

After the die bonding process, the semiconductor package and semiconductor device can be manufactured in the same manner as the conventional method. For example, if necessary, one or more semiconductor chips can be stacked on the die-bonded semiconductor chip, and then wire bonding is performed. Next, the film-like adhesive is thermally cured, and the entire result is sealed with resin. Through these steps, a semiconductor package can be produced. Then, the desired semiconductor device can be manufactured using this semiconductor package.

Figure 6 is a cross-sectional view for explaining manufacturing method (1) in a schematic manner. Here, manufacturing method (1) is shown when using the dicing die bonding sheet 101 shown in Figure 4.

6A shows a laminate (1) 119A obtained in the lamination (1) step. The laminate (1) 119A includes a semiconductor wafer 9 and a dicing die bonding sheet 101 provided on the back surface 9b of the semiconductor wafer 9.
6(b) shows a semiconductor chip assembly (1) 119B with a film-like adhesive obtained in the dividing/cutting process. The semiconductor chip assembly (1) 119B with a film-like adhesive is configured by holding a plurality of semiconductor chips 139' with a film-like adhesive on a support sheet 10, the semiconductor chips 9' and the film-like adhesive 130 provided on the back surface 9b' of the semiconductor chips 9' after cutting.
6(c) shows the state in which the semiconductor chip 139' with the film-like adhesive is detached from the support sheet 10 in the direction of arrow I using a detachment means 7 and picked up in the pick-up (1) process. An example of the detachment means 7 is a vacuum collet. Note that the detachment means 7 is not shown in cross section here. Remaining of the film-like adhesive 130 is suppressed on the first surface 10a of the support sheet 10.
FIG. 6D shows a state in which the semiconductor chip 9' has been die-bonded to the circuit formation surface 5a of the substrate 5 with a film-like adhesive 130 in the die-bonding step.

Figure 6 shows manufacturing method (1) when using dicing die bonding sheet 101, but similar results can be obtained when using other dicing die bonding sheets.

<<Production method (2)>>
The film-like adhesive of one embodiment of the present invention described above can also be used during the manufacture of semiconductor devices by attaching it to a semiconductor wafer before constructing the dicing die bonding sheet of one embodiment of the present invention described above.
In this case, the manufacturing method of the semiconductor device may be, for example,
A lamination (21) process for producing a laminate (21) including a semiconductor wafer and the film-like adhesive provided on the rear surface of the semiconductor wafer using the film-like adhesive;
a lamination (22) step of producing a laminate (22) in which a dicing sheet is attached to the surface (i.e., the second surface) of the film-like adhesive in the laminate (21) opposite to the semiconductor wafer side, thereby forming a laminate (22) in which the dicing sheet and the laminate (21) are laminated in this order (in other words, the dicing sheet, the film-like adhesive, and the semiconductor wafer are laminated in this order in their thickness direction);
a dividing/cutting process for producing semiconductor chips by dividing the semiconductor wafers in the laminate (22), and cutting the film-like adhesive along the dividing points of the semiconductor wafers to produce a semiconductor chip assembly (2) with a film-like adhesive, in which a plurality of semiconductor chips with a film-like adhesive, each of which includes the semiconductor chip and the film-like adhesive after cutting provided on the back surface of the semiconductor chip, are held on the dicing sheet;
a pick-up (2) process for obtaining a semiconductor chip with a film-like adhesive by separating the semiconductor chip with the film-like adhesive in the semiconductor chip assembly with the film-like adhesive from the dicing sheet and picking it up;
and a die bonding step of die bonding the semiconductor chip in the obtained semiconductor chip with film-like adhesive to a circuit formation surface of a substrate using the film-like adhesive in the semiconductor chip with film-like adhesive (sometimes referred to in this specification as "manufacturing method (2)").
In the manufacturing method (2), a semiconductor device can be manufactured in the same manner as the conventional method, except that the film-like adhesive according to one embodiment of the present invention described above is used instead of the conventional film-like adhesive.

<Lamination (21) step>
In the lamination (21) step, one surface (i.e., the first surface) of the film-like adhesive is attached to the back surface of a semiconductor wafer to produce a laminate (21).
This process can be carried out in the same manner as the conventional method of attaching a film adhesive to the back surface of a semiconductor wafer, except that the film adhesive according to one embodiment of the present invention described above is used instead of the conventional film adhesive.

<Lamination (22) step>
In the lamination (22) step, a dicing sheet is attached to the exposed surface (i.e., the second surface) of the film-like adhesive in the laminate (21), thereby producing the laminate (22).
The dicing sheet used in this step may be a known one, and the dicing sheet can be attached to the film-like adhesive by a known method.

The dicing sheet is substantially the same as the support sheet in the dicing die bonding sheet used in manufacturing method (1). Therefore, the laminate (22) obtained in this process is substantially the same as the laminate (1) obtained in manufacturing method (1).

<Divide/Cut Process>
In the dividing/cutting step, the dividing of the semiconductor wafers in the laminate (22) (production of semiconductor chips) and the cutting of the film-like adhesive in the laminate (22) can be carried out in the same manner as in the dividing of the semiconductor wafers in the laminate (1) and the cutting of the film-like adhesive in the laminate (1) in the manufacturing method (1).

The semiconductor chip with a film-like adhesive produced in this step is the same as the semiconductor chip with a film-like adhesive produced in the dividing/cutting step of production method (1).
In the semiconductor chip assembly (2) with a film-like adhesive produced in this step, a plurality of semiconductor chips with a film-like adhesive are held (fixed) in an aligned state on the dicing sheet, and the semiconductor chip assembly (2) with a film-like adhesive is substantially the same as the semiconductor chip assembly (1) with a film-like adhesive produced in the dividing/cutting step of the manufacturing method (1).

<Pickup (2) process>
In the pick-up (2) step, the semiconductor chips with the film-like adhesive in the semiconductor chip assembly with the film-like adhesive (2) can be picked up by detaching them from the dicing sheet using a known method.
The pick-up (2) step can be carried out in the same manner as the pick-up (1) step in the manufacturing method (1), except that a semiconductor chip assembly with a film-like adhesive (2) is used instead of the semiconductor chip assembly with a film-like adhesive (1).

In this process, by using the film-like adhesive according to one embodiment of the present invention described above, even if the dicing sheet does not have a pressure-sensitive adhesive layer for direct contact with the film-like adhesive, it is possible to prevent the film-like adhesive from remaining on the dicing sheet when picking up the semiconductor chip with the film-like adhesive.

<Die bonding process>
The die bonding step is the same as the die bonding step in the manufacturing method (1).

After the die bonding process, the semiconductor package and semiconductor device can be manufactured in the same manner as in manufacturing method (1).

Figure 7 is a cross-sectional view for explaining the manufacturing method (2) in a schematic manner. Here, the manufacturing method (2) is shown when the film-like adhesive 13 shown in Figure 3 is used.

7A shows a laminate (21) 129A obtained in the lamination step (21). The laminate (21) 129A includes a semiconductor wafer 9 and a film-like adhesive 13 provided on the back surface 9b of the semiconductor wafer 9.
7B shows a laminate (22) 129B obtained in the lamination step (22). The laminate (22) 129B is configured by laminating a dicing sheet 20, a film-like adhesive 13, and a semiconductor wafer 9 in this order in the thickness direction.
7(c) shows a semiconductor chip assembly (2) 129C with a film-like adhesive obtained in the dividing/cutting process. The semiconductor chip assembly (2) 129C with a film-like adhesive is configured by holding a plurality of semiconductor chips 139' with a film-like adhesive on a dicing sheet 20, the semiconductor chips 9' each including a film-like adhesive 130 provided on a rear surface 9b' of the semiconductor chip 9' after cutting.
7(d) shows the state in which the semiconductor chip 139' with the film-like adhesive is picked up by being pulled away from the dicing sheet 20 in the direction of arrow I using the pulling means 7 in the pick-up (2) process. Remaining of the film-like adhesive 130 on the first surface 20a of the dicing sheet 20 is suppressed.
FIG. 7E shows a state in which the semiconductor chip 9' has been die-bonded to the circuit formation surface 5a of the substrate 5 with a film-like adhesive 130 in the die-bonding step.

The present invention will be described in more detail below with reference to specific examples. However, the present invention is not limited to the examples shown below.

<Raw materials for resin production>
The full names of the raw materials for producing the resins, which are abbreviated in the present examples and comparative examples, are shown below.
BA: n-butyl acrylate MA: methyl acrylate GMA: glycidyl methacrylate HEA: 2-hydroxyethyl acrylate MMA: methyl methacrylate AA: acrylic acid

<<Raw materials for producing adhesive composition>>
The raw materials used in producing the adhesive composition are shown below.
[Polymer component (a)]
(a)-1: Acrylic resin (weight average molecular weight 800,000, glass transition temperature −28° C.) obtained by copolymerizing BA (55 parts by mass), MA (10 parts by mass), GMA (20 parts by mass) and HEA (15 parts by mass).
(a)-2: Acrylic resin (weight average molecular weight 800,000, glass transition temperature −42° C.) obtained by copolymerizing BA (84 parts by mass), MMA (8 parts by mass), AA (3 parts by mass), and HEA (5 parts by mass).
(a)-3: Acrylic resin having a weight average molecular weight of 700,000.
[Epoxy resin (b1)]
(b1)-1: A mixture of liquid bisphenol A type epoxy resin and acrylic rubber fine particles ("BPA328" manufactured by Nippon Shokubai Co., Ltd., epoxy equivalent 235 g/eq)
(b1)-2: Bisphenol A type epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, softening point 93°C, epoxy equivalent 800 to 900 g/eq)
(b1)-3: o-cresol novolac type epoxy resin ("EOCN-104S" manufactured by Nippon Kayaku Co., Ltd., softening point 90 to 94°C, epoxy equivalent 213 to 223 g/eq)
(b1)-4: Liquid bisphenol F type epoxy resin ("YL983U" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 165 to 175 g/eq)
(b1)-5: o-cresol novolac type epoxy resin ("EOCN-102S" manufactured by Nippon Kayaku Co., Ltd., softening point 55 to 77°C, epoxy equivalent 205 to 217 g/eq)
(b1)-6: Triphenylene type epoxy resin ("EPPN-502H" manufactured by Nippon Kayaku Co., Ltd., softening point 54°C, epoxy equivalent 167g/eq)
(b1)-7: Liquid bisphenol A type epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 184 to 194 g/eq)
(b1)-8: o-cresol novolac type epoxy resin ("EOCN-103S" manufactured by Nippon Kayaku Co., Ltd., softening point 81 to 85°C, epoxy equivalent 209 to 219 g/eq)
(b1)-9: Dicyclopentadiene type epoxy resin ("XD-1000" manufactured by Nippon Kayaku Co., Ltd., softening point 68 to 78°C, epoxy equivalent 245 to 260 g/eq)
(b1)-10: Dicyclopentadiene type epoxy resin (DIC Corporation, "Epicron HP-7200HH", softening point 88 to 98°C, epoxy equivalent 274 to 286 g/eq)
[Thermal curing agent (b2)]
(b2)-1: Dicyandiamide ("ADEKA Hardener EH-3636AS" manufactured by ADEKA Corporation, solid dispersion type latent hardener, softening point 209°C, active hydrogen content 21 g/eq)
(b2)-2: o-cresol novolak resin (DIC Corporation, "Phenolite KA-1160", softening point 80°C, hydroxyl equivalent 117g/eq)
[Curing Accelerator (c)]
(c)-1: 2-phenyl-4,5-dihydroxymethylimidazole ("Curesol 2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd.)
[Filler (d)]
(d)-1: Spherical silica modified with epoxy groups ("Admanano YA050C-MKK" manufactured by Admatechs Co., Ltd., average particle size 50 nm)
[Coupling agent (e)]
(e)-1: A silicate compound to which 3-glycidoxypropyltrimethoxysilane has been added ("MKC Silicate MSEP-2" manufactured by Mitsubishi Chemical Corporation)
(e)-2: Oligomeric silane coupling agent having an epoxy group, a methyl group, and a methoxy group ("X-41-1056" manufactured by Shin-Etsu Silicones, epoxy equivalent: 280 g/eq)
[Crosslinking agent (f)]
(f)-1: Tolylene diisocyanate trimer adduct of trimethylolpropane ("Coronate L" manufactured by Tosoh Corporation)
[Energy ray curable resin (g)]
(g)-1: A mixture of dipentaerythritol hexaacrylate (a hexafunctional UV-curable compound, molecular weight 578) and dipentaerythritol pentaacrylate (a pentafunctional UV-curable compound, molecular weight 525) ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.)
(g)-2: Tricyclodecane dimethylol diacrylate ("KAYARAD R-684" manufactured by Nippon Kayaku Co., Ltd., molecular weight 304)
[Photopolymerization initiator (h)]
(h)-1: 1-Hydroxycyclohexyl phenyl ketone ("IRGACURE (registered trademark) 184" manufactured by BASF)

[Example 1]
<<Production of Film-like Adhesive>>
<Production of Adhesive Composition>
Polymer component (a)-1 (20 parts by mass), epoxy resin (b1)-1 (25 parts by mass), epoxy resin (b1)-2 (35 parts by mass), epoxy resin (b1)-3 (8 parts by mass), heat curing agent (b2)-1 (1.5 parts by mass), curing accelerator (c)-1 (1.5 parts by mass), coupling agent (e)-1 (0.6 parts by mass), crosslinking agent (f)-1 (0.2 parts by mass), energy ray curable resin (g)-1 (8 parts by mass), and photopolymerization initiator (h)-1 (0.2 parts by mass) were dissolved or dispersed in methyl ethyl ketone and stirred at 23 ° C. to produce a heat curable adhesive composition having a total concentration of 50 mass % of all components other than the solvent. Note that the amounts of the components other than the solvent shown here are all amounts of the target product not including the solvent.

<Production of Film Adhesive>
A release film ("SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm) made of polyethylene terephthalate film, one side of which had been subjected to a release treatment by silicone treatment, was used, and the adhesive composition obtained above was applied to the release-treated surface, followed by drying at 100°C for 1 minute, to produce a thermosetting film-like adhesive having a thickness of 20 μm.

<< Manufacturing of dicing die bonding sheets >>
A laminated substrate (manufactured by Achilles Corporation, "HUSL1302", thickness 100 μm, hereinafter sometimes referred to as "PP/EMAA laminated substrate") consisting of a layer of polypropylene (PP) and a layer of ethylene-methacrylic acid copolymer (EMAA) was used as the substrate, and the exposed surface of the film-like adhesive obtained above, opposite to the side having the release film, was attached to the surface of the polypropylene layer to produce a dicing die bonding sheet. This dicing die bonding sheet is a dicing die bonding sheet with a release film, consisting of a support sheet consisting of only the substrate, a film-like adhesive, and a release film, laminated in this order in the thickness direction.

<<Evaluation of film adhesive>>
<Measurement of _D0 >
[Preparation of first test piece]
Two sheets of film-like adhesive having a release film on one side were prepared in the same manner as above.
Next, the two film-like adhesives were irradiated with ultraviolet light using an ultraviolet irradiation device ("RAD-2000 m/12" manufactured by Lintec Corporation) under conditions of an illuminance of 230 mW/cm ² and a light quantity of 120 mJ/cm ² .
Next, the exposed surfaces of the two sheets of film-like adhesive that had been irradiated with ultraviolet light were bonded together to produce a laminate (primary laminate) of two sheets of film-like adhesive having a thickness of 40 μm and release films on both sides. Two sheets of this primary laminate were then produced.

Next, the release film was removed from one side of these two primary laminates, and the newly exposed surfaces of the film-like adhesive were bonded together to produce a four-sheet laminate of film-like adhesive (secondary laminate) having a thickness of 80 μm and release films on both sides. Two sheets of this secondary laminate were then produced.
Next, the release film was removed from one side of these two secondary laminates and the exposed surfaces of the newly produced film-like adhesive were bonded together to produce a laminate of eight film-like adhesives (tertiary laminate) 160 μm thick and with release films on both sides.
Next, this tertiary laminate and the separately prepared primary laminate were used to remove the release film from one side of each laminate and bond the exposed surfaces of the newly produced film-like adhesive together to produce a laminate of 10 film-like adhesive sheets (quaternary laminate) with a thickness of 200 μm and release films on both sides.

Using a dumbbell cutter (Dumbbell's "SDBK-1000"), the fourth laminate obtained above was punched out to the same shape and dimensions as the test piece specified in JIS K7128-3 to produce a first test piece (thickness 200 μm).

[Measurement of _D0 ]
A tear test was performed on the first test piece obtained above using a universal tensile tester (Shimadzu Corporation "AG-IS") in accordance with JIS K7128-3 to measure _D0 . At this time, the distance between the grippers of the first test piece was 60 mm, the tear speed was 200 mm/min, and the sampling time was 10 ms. The results are shown in Table 1.

<Calculation of |ΔT|>
At the same time as the measurement of D ₀ , T _max , D ₁ and 0.6D ₁ were measured, and |ΔT| was calculated from these values. The results are shown in Table 1.

<Evaluation of the effect of suppressing the remaining film-like adhesive when picking up>
[Production of silicon chips with film-like adhesive]
The release film was removed from the film-like adhesive in the dicing/die bonding sheet obtained above.
Using a tape mounter ("Adwill RAD2500" manufactured by Lintec Corporation), the exposed surface of the film-like adhesive in the dicing die bonding sheet after removing the release film was attached to the polished surface of a silicon wafer (diameter 200 mm, thickness 350 μm) whose back surface was a #2000 polished surface. Then, the dicing die bonding sheet was fixed to a ring frame for wafer dicing.

Next, the film-like adhesive was irradiated with ultraviolet light using an ultraviolet irradiator ("RAD-2000 m/12" manufactured by Lintec Corporation) under conditions of an illuminance of 230 mW/cm ² and a light quantity of 120 mJ/cm ² .

Next, the silicon wafer was divided and the film-like adhesive was cut continuously by dicing using a dicing device (DISCO Corporation "DFD6361") to obtain silicon chips with a size of 2 mm x 2 mm. The dicing was performed by setting the dicing blade moving speed to 40 mm/sec and the dicing blade rotation speed to 35,000 rpm, and cutting the dicing die bonding sheet to a region 20 μm deep from the adhesive surface of the substrate (i.e., the entire region in the thickness direction of the film-like adhesive and the region 20 μm deep from the surface of the substrate on the film-like adhesive side). As the dicing blade, DISCO Corporation "Z05-SD2000-D1-90 CC" was used.
As a result of the above, a group of silicon chips with a film-like adhesive was produced using a dicing die bonding sheet, in which a plurality of silicon chips with a film-like adhesive were fixed in an aligned state on a substrate by the film-like adhesive, the silicon chips comprising a silicon chip and a film-like adhesive provided on the back surface of the silicon chip.

[Evaluation of the effect of suppressing the remaining film-like adhesive when picked up]
Using a pick-up die bonding device (Canon Machinery's "BESTEM D-02"), the silicon chips with the film-like adhesive from the group of silicon chips with the film-like adhesive obtained above were picked up by detaching them from the substrate. This pick-up was performed on 100 silicon chips with the film-like adhesive, and one silicon chip with the film-like adhesive was pushed up from the film-like adhesive side by one pin.
Next, the picked-up locations on the support sheet (substrate) were observed using a digital microscope (Keyence Corporation, "VHX-1000"), the number of locations where film-like adhesive with a length of 100 μm or more remained was counted, and the effect of suppressing the remaining of the film-like adhesive at the time of picking was evaluated according to the following criteria. The results are shown in Table 1. In Table 1, the number in parentheses in the corresponding column is the number of locations where the above-mentioned film-like adhesive remained.
(Evaluation criteria)
A: There are 20 or less locations where the film-like adhesive remains.
B: There are 21 or more locations where the film-like adhesive remains.

<Measurement of adhesive strength of cured film adhesive>
[Production of silicon chips with film-like adhesive]
A group of silicon chips with a film-like adhesive was produced in the same manner as in the above-mentioned "Evaluation of the effect of suppressing the remaining film-like adhesive at the time of picking up."

[Preparation of second test piece]
Next, the silicon chip with the film-like adhesive in the group of silicon chips with the film-like adhesive was removed from the substrate and picked up. Then, using a manual die bonder (CAMMAX Precima's "EDB65"), the entire exposed surface (the surface opposite to the silicon chip side) of the film-like adhesive in the silicon chip with the film-like adhesive was pressed onto the surface of a copper plate (thickness 500 μm) to die-bond the silicon chip with the film-like adhesive onto the copper plate. The die-bonding at this time was performed by applying a force of 2.45 N (250 gf) for 3 seconds to the silicon chip with the film-like adhesive heated to 125° C. in a direction perpendicular to the contact surface with the copper plate.
Next, the copper plate after die bonding was heated at 160° C. for 1 hour to thermally cure the film-like adhesive on the copper plate.
As a result of the above, a second test piece was produced, which was configured by laminating a copper plate, a cured film-like adhesive, and a silicon chip in this order in the thickness direction.

[Measurement of adhesive strength of thermoset film adhesive]
Using a bond tester (Dage's "Series 4000"), while the copper plate in the second test piece obtained above was fixed, a force was applied to the aligned portion of the side of the cured product of the film-like adhesive in the second test piece and the side of the silicon chip at a speed of 200 μm/sec in a direction parallel to one side of the cured product. At this time, a stainless steel plate-shaped pressing means was used as a pressing means for applying the force, and the position of the tip of the pressing means on the copper plate side was adjusted to a height of 7 μm from the surface of the copper plate on which the silicon chip was mounted, so that the pressing means did not come into contact with the copper plate. Then, the maximum value of the force applied until the cured product was destroyed, the cured product was peeled off from the copper plate, or the cured product was peeled off from the silicon chip was measured, and the measured value was adopted as the adhesive strength (N/2 mm□) of the cured product. The results are shown in Table 1.

<<Production of film adhesive, production of dicing die bonding sheet, and evaluation of film adhesive>>
[Examples 2 to 3, Comparative Example 1]
Film-like adhesives and dicing die bonding sheets were produced in the same manner as in Example 1, except that either or both of the types and amounts of the components blended during the production of the adhesive composition were changed so that the types and contents of the components contained in the adhesive composition were as shown in Table 1, and the film-like adhesives were evaluated. However, in Examples 2 and 3 in which the adhesive composition did not contain the energy ray curable resin (g), the film-like adhesive was not irradiated with ultraviolet rays during the production of the first test piece and the production of the silicon chip with the film-like adhesive, and further, a polypropylene (PP) substrate (Gunze Ltd.'s "Fanclea LLD #80", thickness 80 μm) was used as the substrate instead of the PP/EMAA laminated substrate. The results are shown in Table 1.

In addition, a "-" in the column for the contained components in Table 1 means that the adhesive composition does not contain that component.

As is clear from the above results, in Examples 1 to 3, even though the support sheet did not have a pressure-sensitive adhesive layer that was in direct contact with the film-like adhesive, the film-like adhesive could be prevented from remaining on the support sheet when picking up the silicon chip with the film-like adhesive. In Examples 1 to 3, |ΔT| was 9.8 or less.
In addition, in Examples 1 to 3, the adhesive strength of the cured film adhesive was 111 N/2 mm or more, which was sufficient. In these Examples, the cured film did not peel off from the silicon chip when the adhesive strength was measured.
On the other hand, in Examples 1 to 3, D ₀ was 167.2 mm or less.

In contrast, in Comparative Example 1, it was not possible to prevent the film adhesive from remaining on the support sheet when picking up the silicon chip with the film adhesive. In Comparative Example 1, |ΔT| was 10.2, which was large.
Furthermore, in Comparative Example 1, the adhesive strength of the cured product of the film-like adhesive was 57 N/2 mm square, which was insufficient.
On the other hand, in Comparative Example 1, D ₀ was 27.5 mm or more.

The present invention can be used in the manufacture of semiconductor devices.

10: Support sheet, 10a: First side of support sheet, 11: Substrate, 13: Film-like adhesive, 101, 102: Dicing die bonding sheet, 90: Cured film-like adhesive, 90a: First side of cured film-like adhesive, 90b: Second side of cured film-like adhesive, 90c: Side of cured film-like adhesive, 91: Copper plate, 92: Silicon chip, 92c: Side of silicon chip, 99: First test piece

Claims (7)

A curable film-like adhesive,
A tear test was carried out on a first test piece which was a laminate of a plurality of sheets of the film-like adhesive and had a thickness of 200 μm in accordance with JIS K7128-3 by a right-angle tear method, with the distance between a pair of gripping tools which gripped and fixed the first test piece being 60 mm, and the tear speed being 200 mm/min. When the displacement amount in the tear direction of the first test piece when the tear strength of the first test piece exhibits a maximum value _Tmax is defined as D1, and the tear strength when the displacement amount is 0.6D1 is defined as T1, the following formula:
ΔT=(T1/0.6)−T _max
The absolute value of ΔT calculated by is 10 N/mm or less,
The film adhesive contains an acrylic resin and an o-cresol novolac epoxy resin,
The glass transition temperature of the acrylic resin is −60 to 70° C.
A film-like adhesive , wherein the content of the acrylic resin is 5 to 40 mass % relative to the total mass of the film-like adhesive . The film-like adhesive according to claim 1 , further comprising an o-cresol novolac resin. 3. The film-like adhesive according to claim 1 or 2, which does not contain a filler. 4. The film-like adhesive according to claim 1, comprising: a cured product of the film-like adhesive having a size of 2 mm x 2 mm and a thickness of 20 μm; a copper plate having a thickness of 500 μm provided over the entire surface of one side of the cured product; and a silicon chip having a thickness of 350 μm provided over the entire surface of the other side of the cured product; wherein a second test piece is prepared in which the side of the cured product and the side of the silicon chip are aligned; and, with the copper plate fixed, a force is applied simultaneously to the aligned portions of the side of the cured product and the side of the silicon chip in the second test piece in a direction parallel to one side of the cured product at a speed of 200 μm/sec., the maximum force applied until the cured product is destroyed, the cured product is peeled off from the copper plate, or the cured product is peeled off from the silicon chip is 100 N/2 mm□ or more . 5. The film-like adhesive according to claim 1 , wherein, when the tear test is conducted, the displacement in the tear direction of the first test piece from when the tear strength of the first test piece reaches a maximum until the first test piece breaks is 15 mm or less . A support sheet and a film-like adhesive provided on one surface of the support sheet,
A dicing/die bonding sheet, wherein the film-like adhesive is the film-like adhesive according to any one of claims 1 to 5 . The dicing-die bonding sheet according to claim 6 , wherein the support sheet consists of only a substrate.

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