JP6967506B2 - Method for manufacturing film-like adhesive composite sheet and semiconductor device - Google Patents

Description

The present invention relates to a film-shaped adhesive composite sheet and a method for manufacturing a semiconductor device.
This application claims priority based on Japanese Patent Application No. 2016-031641 filed in Japan on February 23, 2016, the contents of which are incorporated herein by reference.

In the manufacturing process of a semiconductor device, a semiconductor chip to which a film-like adhesive for use in die bonding may be attached may be used. As one of the methods for obtaining such a semiconductor chip with a film-like adhesive, a film-like adhesive is attached to a plurality of pre-divided semiconductor chips by dicing a semiconductor wafer, and then the film-like adhesive is applied. There is a method of cutting at a position corresponding to the arrangement position of the semiconductor chip. In this method, usually, a film-like adhesive composite sheet in which a film-like adhesive is provided on a support sheet is used, and one film-like adhesive is attached to a plurality of semiconductor chips. A semiconductor chip is manufactured, for example, by forming a groove from the front surface of a semiconductor wafer and then grinding the back surface side until the groove is reached. This is an example, and the semiconductor chip is also manufactured by another method. NS. The semiconductor chip to which the film-shaped adhesive after cutting is attached is separated (picked up) from the support sheet together with the film-shaped adhesive and used for die bonding.

In the above method, as a method of cutting the film-shaped adhesive, for example, a method of irradiating the film-shaped adhesive with a laser to cut the film-shaped adhesive and a method of cutting by expanding the film-shaped adhesive are known. .. However, the method of irradiating a laser requires a laser irradiation device and has a problem that it cannot be cut efficiently in a short time. Further, the expanding method requires an expanding device and has a problem that the cut surface may be roughened. Further, in the expand, the force acts only in the direction of the same surface as the film-like adhesive, so that the film-like adhesive may only stretch together with the support sheet and not be cut. Therefore, the film-like adhesive may be cooled to make it easier to cut and expand, but in this case, a cooling step is required and the productivity is inferior.

As a method that can solve these problems, a film-like adhesive having a specific thickness and tensile elongation at break is used, and the semiconductor chip is picked up together with this uncut film-like adhesive at the stage immediately before the pickup of the semiconductor chip. A method of cutting a film-like adhesive by lifting it in a direction and utilizing the shearing force generated at that time is disclosed (see Patent Document 1).

Japanese Unexamined Patent Publication No. 2013-179317

However, in the method disclosed in Patent Document 1, it is not clear whether or not the semiconductor chip to which the film-like adhesive after cutting is attached can be picked up from the support sheet by suppressing the occurrence of process abnormalities.

The present invention has been made in view of the above circumstances, and a semiconductor chip to which a film-like adhesive is attached is suppressed from the occurrence of process abnormalities by a simplified method at the time of manufacturing a semiconductor device. An object of the present invention is to provide a film-shaped adhesive composite sheet in which a film-shaped adhesive is provided on the support sheet, which can be separated from the support sheet, and a method for manufacturing a semiconductor device using the composite sheet.

In order to solve the above problems, the present invention is a film-like adhesive composite sheet in which a curable film-like adhesive having a thickness of 1 to 50 μm is provided on a support sheet having a base material, and the present invention is a film-like adhesive composite sheet before curing. Adhesive strength A (N / 24 mm) of the film-like adhesive to a semiconductor wafer, and break elongation B (%) of a laminate obtained by laminating the film-like adhesive before curing so that the total thickness is 200 μm. , And a film-like adhesive composite sheet in which the breaking strength C (MPa) of the laminated body satisfies the relationship of the following formula (1).
A / (B × C) ≧ 0.0005 ・ ・ ・ ・ (1)

In the film-shaped adhesive composite sheet of the present invention, the breaking elongation B is preferably 500% or less.
In the film-shaped adhesive composite sheet of the present invention, it is preferable that the support sheet is made of the base material and the film-shaped adhesive is provided in direct contact with the base material.
Further, the present invention is a method for manufacturing a semiconductor device using the film-shaped adhesive composite sheet, wherein the film-shaped adhesive composite sheet is formed into a plurality of semiconductor chips already divided via a film-shaped adhesive. By applying a force to the step of attaching and the support sheet of the film-like adhesive composite sheet attached to the semiconductor chip from the side opposite to the side where the film-like adhesive is provided, the force is applied through the support sheet. It has a step of applying a force to the film-shaped adhesive to cut the film-shaped adhesive, and a step of separating the semiconductor chip and the cut film-shaped adhesive attached to the semiconductor chip from the support sheet. , Provide a method for manufacturing a semiconductor device.

That is, the present invention includes the following aspects.
[1] A film-like adhesive composite sheet,
In the film-like adhesive composite sheet, a curable film-like adhesive having a thickness of 1 to 50 μm is provided on a support sheet having a base material;
The adhesive strength of the film-shaped adhesive before curing to the semiconductor wafer is set to adhesive strength A (N / 24 mm), and the film-shaped adhesive before curing is laminated so that the total thickness is 200 μm. A film-like adhesive composite sheet satisfying the relationship of the following formula (1) when the breaking elongation is defined as breaking elongation B (%) and the breaking strength of the laminated body is defined as breaking strength C (MPa).
A / (B × C) ≧ 0.0005 ・ ・ ・ ・ (1)
[2] The film-like adhesive composite sheet according to [1], wherein the elongation at break B is 500% or less.
[3] The film-shaped adhesive composite sheet according to [1] or [2], wherein the support sheet is made of the base material, and the film-shaped adhesive is provided in direct contact with the base material.
[4] A method for manufacturing a semiconductor device.
A step of attaching the film-shaped adhesive composite sheet according to any one of [1] to [3] to a plurality of semiconductor chips that have been divided via the film-shaped adhesive.
By applying a force to the support sheet in the film-like adhesive composite sheet attached to the semiconductor chip from the side opposite to the side on which the film-like adhesive is provided, the film-like adhesive sheet is passed through the support sheet. The step of applying force to the adhesive to cut the film-like adhesive, and
A step of separating the semiconductor chip and the film-like adhesive after cutting attached to the semiconductor chip from the support sheet, and
A method for manufacturing a semiconductor device, including.

According to the present invention, it is possible to suppress the occurrence of process abnormalities and separate the semiconductor chip to which the film-like adhesive is attached from the support sheet by a simplified method at the time of manufacturing the semiconductor device. Provided are a film-shaped adhesive composite sheet in which a film-shaped adhesive is provided on a support sheet, and a method for manufacturing a semiconductor device using the composite sheet.

It is sectional drawing which shows 1 Embodiment in the manufacturing method of the semiconductor device of this invention from the cutting of a film-like adhesive to the separation of a semiconductor chip from a support sheet. It is sectional drawing for schematically explaining another embodiment which applies a force to a film-like adhesive and cuts it in the manufacturing method of the semiconductor device of this invention. It is sectional drawing which shows typically one aspect of the film-like adhesive composite sheet and the semiconductor chip in the manufacturing process of the semiconductor device in the case of using the conventional film-like adhesive composite sheet. It is sectional drawing which shows typically the other aspect of the film-like adhesive composite sheet and the semiconductor chip in the manufacturing process of the semiconductor device when the conventional film-like adhesive composite sheet is used.

<< Film-like adhesive composite sheet >>
The film-shaped adhesive composite sheet of the present invention is a film-shaped adhesive composite sheet in which a curable film-shaped adhesive having a thickness of 1 to 50 μm is provided on a support sheet having a base material, and is a film-shaped adhesive composite sheet before curing. The adhesive force of the film-like adhesive to the semiconductor wafer is defined as the adhesive force A (N / 24 mm), and the elongation at break of the laminated body obtained by laminating the film-like adhesive before curing so as to have a total thickness of 200 μm. When the breaking elongation B (%) and the breaking strength of the laminated body are the breaking strength C (MPa), A, B, and C satisfy the relationship of the following formula (1).
A / (B × C) ≧ 0.0005 ・ ・ ・ ・ (1)

The film-like adhesive composite sheet is attached to one surface of the semiconductor chip (mainly the back surface opposite to the circuit surface) by the film-like adhesive at the time of manufacturing the semiconductor device. In a later step, the semiconductor chip is pulled away (picked up) from the support sheet with the film-like adhesive still attached.
At this time, the film-like adhesive provided on the film-like adhesive composite sheet satisfies the relationship of the above formula (1), so that the semiconductor chip to which the film-like adhesive is attached has a process abnormality. Can be suppressed and separated from the support sheet. More specifically, it is as follows.

First, according to the film-shaped adhesive composite sheet of the present invention, a step mainly aimed at cutting the film-shaped adhesive is separately performed by performing a normal operation of applying a force to the film-shaped adhesive through the support sheet. Even if it is not provided, the film-like adhesive can be cut at a desired location at room temperature. Therefore, the defect of separating (lifting) the semiconductor chip due to the film-like adhesive not being cut is suppressed.
Further, the phenomenon that the portion corresponding to the target semiconductor chip in the film-shaped adhesive is peeled off from the support sheet and the portion corresponding to the unintended semiconductor chip in the film-shaped adhesive is peeled off from the support sheet is suppressed. NS. Therefore, the semiconductor chip cannot be separated (lifted) poorly because the target portion of the film-like adhesive does not peel off from the support sheet, and not only the target semiconductor chip but also the semiconductor chip adjacent to the target semiconductor chip is simultaneously coated with the film-like adhesive. At the same time, the generation of so-called double dies, which are separated from the support sheet, is suppressed.

As described above, by using the film-shaped adhesive composite sheet, it is possible to suppress the defective separation of the semiconductor chip and the occurrence of double dies. Further, a step mainly for cutting the film-shaped adhesive as described above, for example, a step of irradiating the film-shaped adhesive with a laser to cut the film-shaped adhesive, a step of cutting by expanding the film-shaped adhesive, and the like are performed. Since it can be omitted, the problems caused by performing these steps can be avoided, the film-like adhesive can be cut at room temperature, the number of steps can be reduced, and the semiconductor device can be manufactured by a simplified method.

On the other hand, in the above-mentioned "Japanese Unexamined Patent Publication No. 2013-179317" (Patent Document 1), the semiconductor chip is lifted together with the uncut film-like adhesive in the pickup direction at the stage immediately before the pickup of the semiconductor chip. , A method of cutting a film-like adhesive by utilizing the shearing force generated at that time is disclosed. However, in this method, it is not clear whether or not the semiconductor chip to which the film-like adhesive after cutting is attached can be picked up from the support sheet by suppressing the occurrence of process abnormalities. For example, it is uncertain whether the semiconductor chip will be pulled away from the support sheet with the film-like adhesive after cutting normally provided. In the examples of this document, a film-like adhesive composite sheet in which a film-like adhesive is provided on a general dicing sheet (a support sheet having a base material and a pressure-sensitive adhesive layer) is specifically disclosed. It is not disclosed that the above-mentioned effects of the present invention are exhibited.

<Support sheet>
The support sheet has a base material, may be made of a base material (has only a base material), or may have a base material and a layer other than the base material. .. Examples of the support sheet having the other layer include those having an adhesive layer on the base material.
The film-like adhesive described later is provided on the support sheet. Therefore, for example, when the support sheet is provided with the pressure-sensitive adhesive layer on the base material, the film-like adhesive is provided on the pressure-sensitive adhesive layer, and the support sheet is made of the base material. Is provided with a film-like adhesive in direct contact with the substrate.

[Base material]
The constituent material of the base material is preferably various resins, and specifically, for example, polyethylene (low density polyethylene (may be abbreviated as LDPE), linear low density polyethylene (may be abbreviated as LLDPE)). , High-density polyethylene (HDPE (sometimes abbreviated), etc.)), Polypropylene, Polybutene, Polybutadiene, Polymethylpentene, styrene / ethylenebutylene / styrene block copolymer, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate , Polybutylene terephthalate, polyurethane, polyurethane acrylate, polyimide, ethylene vinyl acetate copolymer, ionomer resin, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer, polystyrene, polycarbonate, fluorine Examples thereof include a resin, a water additive, a modified product, a crosslinked product, or a copolymer of any of these resins.

In addition, in this specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth) acrylic acid, for example, "(meth) acrylate" is a concept that includes both "acrylate" and "methacrylate", and is a "(meth) acryloyl group". Is a concept that includes both "acryloyl group" and "methacryloyl group".

The resin constituting the base material may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

The base material may be composed of one layer (single layer) or may be composed of two or more layers. When the base material is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.
In the present specification, not only in the case of a base material, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers are different". It may be, and only some of the layers may be the same. ”Furthermore,“ a plurality of layers are different from each other ”means that“ at least one of the constituent materials and the thickness of each layer is different from each other ”. Means.

The thickness of the base material can be appropriately selected depending on the intended purpose, but is preferably 50 to 300 μm, more preferably 60 to 100 μm.
Here, the "thickness of the base material" means the thickness of the entire base material, and for example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material. means.
In addition, in this specification, "thickness" means the value represented by the average of the thickness measured by the contact type thickness gauge at arbitrary 5 places.

In order to improve the adhesion of the base material to other layers such as the pressure-sensitive adhesive layer provided on the base material, the base material is subjected to sandblasting treatment, solvent treatment or other unevenness treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment. , Ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments may be applied to the surface.
Further, the base material may have a surface surface treated with a primer.
In addition, the base material prevents the base material from adhering to other sheets and the base material from adhering to the adsorption table when the antistatic coat layer and the film-like adhesive composite sheet are laminated and stored. It may have a layer or the like.
Among these, the base material is particularly preferably one whose surface has been subjected to electron beam irradiation treatment from the viewpoint of suppressing the generation of fragments of the base material due to the friction of the blade during dicing.

[Adhesive layer]
As the pressure-sensitive adhesive layer, a known one can be appropriately used.
The pressure-sensitive adhesive layer can be formed by using a pressure-sensitive adhesive composition containing various components for constituting the pressure-sensitive adhesive layer. The ratio of the contents of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components in the pressure-sensitive adhesive layer. In addition, in this specification, "normal temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

When the pressure-sensitive adhesive layer contains an energy ray-curable component, the semiconductor chip can be more easily picked up by irradiating the pressure-sensitive adhesive layer with energy rays to reduce the adhesiveness. The treatment of irradiating the adhesive layer with energy rays to reduce the adhesiveness may be performed after the film-shaped adhesive composite sheet is attached to the adherend, or may be performed in advance before the adhesive layer is attached to the adherend. You may.

In the present invention, the "energy beam" means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays and electron beams.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, or the like as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
In the present invention, "energy ray curable" means a property of being cured by irradiating with energy rays, and "non-energy ray curable" means a property of not being cured by irradiating with energy rays. ..

Preferred adhesive compositions include, for example, an acrylic polymer and an energy ray-polymerizable compound (adhesive composition (i); having a hydroxyl group and having a polymerizable group in the side chain. Examples thereof include an acrylic polymer (for example, one having a hydroxyl group and having a polymerizable group in a side chain via a urethane bond) and an isocyanate-based cross-linking agent (adhesive composition (ii)). It is preferable that the polymer contains a polymer.

In addition to the above-mentioned components, the pressure-sensitive adhesive composition further comprises various additives such as a photopolymerization initiator, a colorant (pigment, dye), a deterioration inhibitor, an antistatic agent, a flame retardant, a silicone compound, and a chain transfer agent. It may contain any of the above.

The pressure-sensitive adhesive composition may contain a reaction retarder for suppressing the progress of an unintended cross-linking reaction during storage. Examples of the reaction retarder include those that inhibit the action of a component that serves as a catalyst for advancing the crosslinking reaction, and preferred examples include those that form a chelate complex by chelating to the catalyst. More specifically, a preferable reaction retarder includes one having two or more carbonyl groups (-C (= O)-) in the molecule, and any agent having two or more carbonyl groups in the molecule. For example, dicarboxylic acid, keto acid, diketone and the like can be mentioned.

The thickness of the pressure-sensitive adhesive layer can be appropriately selected depending on the intended purpose, but is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.

The pressure-sensitive adhesive composition is obtained by blending each component for constituting the pressure-sensitive adhesive layer such as an acrylic polymer. For example, the pressure-sensitive adhesive composition is the same as that of the adhesive composition described later except that the blending components are different. Obtained by the method.

The pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive composition to the surface of the base material and drying it.
At this time, if necessary, the coated pressure-sensitive adhesive composition may be crosslinked by heating. The heating conditions can be, for example, 1 minute to 5 minutes at 100 to 130 ° C., but are not limited thereto. It is also possible to apply the pressure-sensitive adhesive composition to the peel-processed surface of the release film and dry it to bond the pressure-sensitive adhesive layer to the surface of the base material and remove the release film as necessary. An adhesive layer can be formed on the material.

The surface of the base material of the pressure-sensitive adhesive composition or the surface of the release layer of the release material may be coated by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, or a roll knife. Examples thereof include a method using various coaters such as a coater, a curtain coater, a die coater, a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.

<Film-like adhesive>
The film-like adhesive has curability. The film-like adhesive preferably has thermosetting property, and preferably has pressure-sensitive adhesive property. The film-like adhesive having both thermosetting property and pressure-sensitive adhesive property can be attached by lightly pressing against various adherends in an uncured state. Further, the film-like adhesive may be one that can be attached to various adherends by heating and softening the adhesive. The film-like adhesive eventually becomes a cured product having high impact resistance by curing, and this cured product can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

The thickness of the film-like adhesive is 1 to 50 μm, preferably 3 to 25 μm, and more preferably 5 to 15 μm. When the thickness of the film-shaped adhesive is at least the above lower limit value, high adhesive force to the adherend (semiconductor chip) can be obtained. Further, since the thickness of the film-shaped adhesive is not more than the above upper limit value, it is generated by this operation by performing an operation of applying a force to the film-shaped adhesive through the support sheet, which is usually performed at the time of manufacturing a semiconductor device. The film-like adhesive can be easily cut by utilizing the shearing force, and it is not necessary to separately provide a step mainly for cutting the film-like adhesive.

In the present invention, the "adhesive force A (N / 24 mm)" of the film-like adhesive to the semiconductor wafer before curing means a value measured by the following method. That is, a laminated sheet of a film-like adhesive and an adhesive tape having a width of 24 mm and an arbitrary length is produced. This laminated sheet is assumed to have a film-like adhesive laminated on the adhesive surface of the adhesive tape, and the adhesive tape is, for example, "Cellotape (registered trademark) No. 405" manufactured by Nichiban Co., Ltd. having a width of 24 mm. Can be used. Next, the laminated sheet is attached to the semiconductor wafer by a film-like adhesive heated to 60 ° C. to prepare a laminated body in which the adhesive tape, the film-like adhesive and the semiconductor wafer are laminated in this order. Immediately after the laminated body after production is left for 30 minutes under the standard environment specified in JIS Z0237 2009, a laminated sheet of a film-like adhesive and an adhesive tape is applied from the semiconductor wafer to each other of the film-like adhesive and the semiconductor wafer. The so-called 180 ° peeling is performed by peeling at a peeling speed of 150 mm / min so that the surfaces that have been in contact with each other form an angle of 180 °. The peeling force at this time is measured, and the measured value is defined as the adhesive force A (N / 24 mm). The length of the laminated sheet used for measurement is not particularly limited as long as the peeling force can be stably measured.

The adhesive strength A is not particularly limited as long as the relationship of the above formula (1) is satisfied, but is preferably 0.3 N / 24 mm or more, and more preferably 0.4 N / 24 mm or more. The upper limit of the adhesive force A can be, for example, 15N / 24mm, 11N / 24mm, and 7N / 24mm, but these are examples.
For example, the adhesive strength A is preferably 0.3N / 24mm to 15N / 24mm, more preferably 0.3N / 24mm to 11N / 24mm, and even more preferably 0.4N / 24mm to 7N / 24mm.
As another aspect, the adhesive force A may be 0.45N / 24mm or more and less than 10N / 24mm, and may be 0.45N / 24mm or more and 5.8N / 24mm or less.

In the present invention, the "breaking elongation B (%)" means the breaking elongation of a laminate obtained by laminating the film-shaped adhesive before curing so that the total thickness is 200 μm. do. In the present invention, the breaking elongation of the film-like adhesive or the laminated body obtained by laminating the same, including the breaking elongation B, is JIS K711-1994 (ISO 527-1) or JIS K7127: 1999 (. It was obtained in accordance with ISO 527-3). When the object to be measured (test piece) does not have a yield point, the tensile fracture strain is measured, and when it has a yield point, the nominal strain at the time of tensile fracture is measured, and these measured values are used to measure the fracture elongation. Ask for.

The laminated body for which the elongation at break B is to be obtained has a thickness of less than 200 μm and a thickness of 1 to 50 μm for forming a film-like adhesive before curing, preferably a film-like adhesive composite sheet of the present invention. It is obtained by laminating at least two sheets of the film-like adhesive before curing so as to have a total thickness of 200 μm.

The breaking elongation B is such that the laminated body (test piece) of the film-like adhesive having a width of 15 mm, a length of 100 mm, and a thickness of 200 μm is fixed at a distance of 75 mm. It is obtained by fixing at two places, setting a tensile speed of 200 mm / min, pulling the laminated body between the fixed places, and measuring the elongation of the test piece when the laminated body breaks.
In the present specification, "the breaking elongation B is X% (X is a positive number in the formula)" means that the test piece (laminated body) is pulled by the above-mentioned measuring method. Is extended by X% of its original length (length when not pulled) in its tensile direction, that is, the total length of the test piece in the tensile direction is the length before pulling [1 + X]. / 100] means that the test piece breaks when it is multiplied.

The elongation at break B is not particularly limited as long as the relationship of the above formula (1) is satisfied, but is preferably 1200% or less, more preferably 30 to 1200%, and 40 to 1100%, for example. Is more preferable, and 45 to 1050% is particularly preferable. When the breaking elongation B is not more than the upper limit value, the film-like adhesive can be cut more easily before picking up the semiconductor chip to which the film-like adhesive is attached.

Further, as another aspect, the elongation at break B is preferably 900% or less, more preferably 700% or less, particularly preferably 500% or less, for example, 30 to 500%, 40. It can be any of ~ 500%, 45 ~ 500% and the like.
As yet another aspect, the elongation at break B may be 50 to 440%.
When the breaking elongation B is not more than the upper limit value, the film-like adhesive can be more easily cut by various methods before picking up the semiconductor chip to which the film-like adhesive is attached. That is, as the cutting method of the film-shaped adhesive, not only the most general pin-pushing method but also other methods such as the slider-pushing method can be suitably applied, and the versatility of the film-shaped adhesive composite sheet is increased.

In the present invention, the "breaking strength C (MPa)" means the breaking strength of the laminated body obtained by laminating the film-shaped adhesive before curing so that the total thickness is 200 μm. The laminated body referred to here means the same laminated body as the laminated body for which the above-mentioned breaking elongation B (%) is to be measured.
The breaking strength C is the tensile stress when the test piece is broken (broken) at the time of measuring the breaking elongation B, that is, the tensile breaking stress, and can be measured at the same time as the breaking elongation B.

The breaking strength C is not particularly limited as long as the relationship of the above formula (1) is satisfied, but is preferably 0.4 to 17 MPa, more preferably 0.5 to 15 MPa, and 0.6 to 13 MPa. Is particularly preferred.
As another aspect, the breaking strength C may be 0.8 to 11 MPa or 2.5 to 11 MPa.

In the present invention, the adhesive force A, the breaking elongation B and the breaking strength C may satisfy the relationship of the above formula (1), that is, the value of A / (B × C) may be 0.0005 or more. The value of A / (B × C) is preferably 0.0006 or more, and more preferably 0.0007 or more. The upper limit of A / (B × C) is not particularly limited and may be, for example, any of 0.0170, 0.0140 and 0.0115, but these are examples.
That is, the value of A / (B × C) may be, for example, 0.0005 or more and 0.0170 or less, preferably 0.0006 or more and 0.0140 or less, and 0.00067 or more and 0.0115 or less. As another aspect more preferable than the following, the value of A / (B × C) may be 0.0008 or more and less than 0.0125, or may be 0.0008 or more and 0.0105 or less.

The adhesive force A of the film-like adhesive is the type and amount of components contained in the film-like adhesive, the thickness of the film-like adhesive, the material constituting the surface of the support sheet on which the film-like adhesive is provided, and the surface of this surface. It can be adjusted as appropriate by adjusting the state (surface state) and the like.
For example, in the case of a component contained in a film-shaped adhesive, the adhesive strength A of the film-shaped adhesive can be easily adjusted by adjusting the type or amount of the coupling agent (e) such as the silane coupling agent described later. ..
Further, for example, the surface condition of the support sheet is, for example, the surface treatment mentioned above as a substance for improving the adhesion with other layers of the base material, that is, an uneven treatment by sandblasting, solvent treatment, or the like; corona. It can be adjusted by performing oxidation treatment such as discharge treatment, electron beam irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment; and primer treatment.
However, these adjustment methods are only an example.

The breaking elongation B and breaking strength C of the film-shaped adhesive can be appropriately adjusted by adjusting the type and amount of the components contained in the film-shaped adhesive. For example, the molecular weight and content of the polymer component (a) described later, the structure of the components constituting the epoxy thermosetting resin (b), the softening point and the content, the content of the filler (c) and the like are adjusted. By doing so, the breaking elongation B and the breaking strength C of the film-like adhesive can be easily adjusted.
However, these adjustment methods are only an example.

[Adhesive composition]
The film-like adhesive can be formed from an adhesive composition containing the constituent material. For example, the film-like adhesive can be formed on a target portion by applying the adhesive composition to the surface to be formed of the film-like adhesive and drying it if necessary. 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 of the film-like adhesive. Here, "normal temperature" is as described above.

The coating of the adhesive composition may be carried out by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, and a screen coater. , A method using various coaters such as a Meyer bar coater and a knife coater.

The drying conditions of the adhesive composition are not particularly limited, but when the adhesive composition contains a solvent described later, it is preferably heat-dried. In this case, for example, at 70 to 130 ° C. for 10 seconds to dry. It is preferable to dry under the condition of 5 minutes.

Preferred adhesive compositions include, for example, those containing a polymer component (a) and an epoxy-based thermosetting resin (b). Hereinafter, each component will be described.

(Polymer component (a))
The polymer component (a) is a component that can be regarded as being formed by a polymerization reaction of a polymerizable compound, and imparts film-forming property, flexibility, etc. to the film-like adhesive and is attached to an object to be bonded such as a semiconductor chip. It is a polymer compound for improving adhesiveness (stickability). Further, the polymer component (a) is also a component that does not correspond to the epoxy resin (b1) and the thermosetting agent (b2) described later.

As the polymer component (a), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.

Examples of the polymer component (a) include an acrylic resin (for example, a resin having a (meth) acryloyl group), a polyester, a urethane resin (for example, a resin having a urethane bond), an acrylic urethane resin, and a silicone resin (for example, a resin having a urethane bond). For example, a resin having a siloxane bond), a rubber resin (for example, a resin having a rubber structure), a phenoxy resin, a thermosetting polyimide and the like can be mentioned, and an acrylic resin is preferable.

Examples of the acrylic resin in the polymer component (a) include known acrylic polymers.
The weight average molecular weight (Mw) of the acrylic resin is preferably 1000 to 2000000, and more preferably 100,000 to 1500,000. When the weight average molecular weight of the acrylic resin is within such a range, it becomes easy to adjust the adhesive force A of the film-like adhesive within the above-mentioned range.
On the other hand, when the weight average molecular weight of the acrylic resin is at least the above lower limit value, the shape stability (stability over time during storage) of the film-like adhesive is improved. Further, when the weight average molecular weight of the acrylic resin is not more than the above upper limit value, the film-like adhesive can easily follow the uneven surface of the adherend, and voids or the like can be formed between the adherend and the film-like adhesive. Is more suppressed.
In the present specification, the "weight average molecular weight" is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70 ° C, more preferably -30 to 50 ° C. When the Tg of the acrylic resin is at least the above lower limit value, the adhesive force between the film-like adhesive and the support sheet is suppressed, and the semiconductor chip provided with the film-like adhesive is separated from the support sheet at the time of pickup. Will be easier. Further, when the Tg of the acrylic resin is not more than the upper limit value, the adhesive force between the film-like adhesive and the semiconductor chip is improved.
As used herein, the "glass transition temperature" is represented by the temperature of the inflection point of the obtained DSC curve obtained by measuring the DSC curve of the sample using a differential scanning calorimeter.

Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and (meth) acrylic acid. ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , (Meta) undecyl acrylate, (meth) dodecyl acrylate (also called (meth) lauryl acrylate), (meth) tridecyl acrylate, (meth) tetradecyl acrylate (also called (meth) myristyl acrylate), ( Alkyl such as pentadecyl acrylate, hexadecyl (meth) acrylate (also referred to as palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also referred to as stearyl acrylate). The alkyl group constituting the ester is a (meth) acrylic acid alkyl ester having a chain structure having 1 to 18 carbon atoms;
(Meta) Acrylic acid cycloalkyl esters such as (meth) acrylate isobornyl, (meth) acrylate dicyclopentanyl;
(Meta) Acrylic acid aralkyl esters such as benzyl (meth) acrylic acid;
(Meta) Acrylic acid cycloalkenyl ester such as (meth) acrylic acid dicyclopentenyl ester;
(Meta) Acrylic acid cycloalkenyloxyalkyl ester such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meta) Acrylic acid imide;
A glycidyl group-containing (meth) acrylic acid ester such as glycidyl (meth) acrylate;
(Meta) hydroxymethyl acrylate, (meth) 2-hydroxyethyl acrylate, (meth) 2-hydroxypropyl acrylate, (meth) 3-hydroxypropyl acrylate, (meth) 2-hydroxybutyl acrylate, (meth) ) Hydroxyl-containing (meth) acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate;
Examples thereof include substituted amino group-containing (meth) acrylic acid esters such as N-methylaminoethyl (meth) acrylic acid. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.
Among the above, butyl acrylate, methyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate and the like are preferable.

The acrylic resin is, for example, one or more selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide and the like, in addition to the (meth) acrylic acid ester. The monomer may be copolymerized.

The monomer constituting the acrylic resin may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

The acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group and an isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a cross-linking agent (f) described later, or may be directly bonded to another compound without a cross-linking agent (f). .. When the acrylic resin is bonded to other compounds by the functional group, the reliability of the package obtained by using the film-shaped adhesive composite sheet tends to be improved.

In the present invention, as the polymer component (a), a thermoplastic resin other than the acrylic resin (hereinafter, may be simply abbreviated as “thermoplastic resin”) is used alone without using the acrylic resin. It may be used in combination with an acrylic resin. By using the thermoplastic resin, it becomes easier to separate the semiconductor chip provided with the film-like adhesive from the support sheet at the time of pickup, and the film-like adhesive easily follows the uneven surface of the adherend. Therefore, the generation of voids and the like may be further suppressed between the adherend and the film-like adhesive.

The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100,000, more preferably 3000 to 80000.

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

Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene and the like.

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

The content of the acrylic resin as the polymer component (a) is based on the total mass of all the components other than the solvent constituting the adhesive composition (that is, the total mass of the film-like adhesive). It is preferably 5 to 40% by mass, more preferably 7 to 25% by mass.

The ratio of the content of the polymer component (a) is not limited to the type of the polymer component (a), and is based on the total mass of all the components other than the solvent constituting the adhesive composition (that is, film-like adhesion). It is preferably 5 to 85% by mass, more preferably 7 to 80% by mass, based on the total mass of the agent.

While the above-mentioned effects can be obtained by using the thermoplastic resin, when the film-like adhesive before curing is exposed to a high temperature (for example, 120 ° C. to 200 ° C.), its hardness is lowered and the film-like adhesive is not yet cured. There is a concern that the wire bonding suitability of the film-like adhesive in a cured or semi-cured state may decrease. Therefore, it is preferable to set the content of the polymer component (a) in the adhesive composition in consideration of such an influence.

(Epoxy-based thermosetting resin (b))
The epoxy-based thermosetting resin (b) is composed of an epoxy resin (b1) and a thermosetting agent (b2).
The epoxy-based thermosetting resin (b) contained in the adhesive composition and the film-like adhesive may be of only one type, may be of two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.

-Epoxy resin (b1)
Examples of the epoxy resin (b1) include known ones, such as polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, dicyclopentadiene type epoxy resin, and the like. Examples thereof include biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, and other bifunctional or higher functional epoxy compounds.
Among the above, bisphenol A type epoxy resin, phenylene skeleton type epoxy resin (for example, triphenylene type epoxy resin), dicyclopentadiene type epoxy resin and the like are preferable.

As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group may be used. Epoxy resins having unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins having no unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the film-shaped adhesive composite sheet is improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting a part of the epoxy group of the polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by subjecting an epoxy group to an addition reaction of (meth) acrylic acid or a derivative thereof. As used herein, the term "derivative" means a compound in which at least one group of the original compound is substituted with another group (substituent) unless otherwise specified. Here, the "group" includes not only an atomic group formed by bonding a plurality of atoms but also one atom.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound 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 (also referred to as a vinyl group), a 2-propenyl group (also referred to as an allyl group), and a (meth) acryloyl group. , (Meta) acrylamide group and the like, and an acryloyl group is preferable.

The number average molecular weight of the epoxy resin (b1) is not particularly limited, but is preferably 300 to 30,000 from the viewpoint of the curability of the film-shaped adhesive and the strength and heat resistance of the film-shaped adhesive after curing.
As used herein, "number average molecular weight" means a number average molecular weight represented by a standard polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method, unless otherwise specified.
The epoxy equivalent of the epoxy resin (b1) is preferably 100 to 1000 g / eq, more preferably 150 to 800 g / eq.
As used herein, "epoxy equivalent" means the number of grams (g / eq) of an epoxy compound containing 1 gram equivalent of an epoxy group and can be measured according to the method of JIS K 7236: 2001.

As the epoxy resin (b1), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.

-Thermosetting agent (b2)
The thermosetting agent (b2) functions as a curing agent for the epoxy resin (b1).
Examples of the thermosetting agent (b2) include compounds having at least two functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group is annealed, and the like, and the phenolic hydroxyl group, an amino group, or an acid group is annealed. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (b2), examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resin, biphenol, novolak type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, and aralkyl type phenol. Examples include resin. Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter, may be abbreviated as "DICY") and the like.

The thermosetting agent (b2) may have an unsaturated hydrocarbon group.
The thermosetting agent (b2) having an unsaturated hydrocarbon group is, for example, a compound in which a part of the hydroxyl group of the phenol resin is replaced with a group having an unsaturated hydrocarbon group, which is not suitable for the aromatic ring of the phenol resin. Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (b2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

When a phenolic curing agent is used as the thermosetting agent (b2), the thermosetting agent (b2) is softened from the viewpoint that the adhesive force A of the film-like adhesive can be easily adjusted within the above-mentioned range. Those having a high point or glass transition temperature are preferable.

The molecular weight of the thermosetting agent (b2) is preferably, for example, 60 to 30,000.

As the thermosetting agent (b2), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.

In the adhesive composition and the film-like adhesive, the content of the thermosetting agent (b2) is preferably 0.1 to 500 parts by mass with respect to 100 parts by mass of the content of the epoxy resin (b1). It is more preferably 1 to 200 parts by mass. When the content of the thermosetting agent (b2) is at least the lower limit value, the curing of the film-like adhesive becomes easier to proceed. Further, when the content of the thermosetting agent (b2) is not more than the upper limit value, the hygroscopicity of the film-shaped adhesive is reduced, and the reliability of the package obtained by using the film-shaped adhesive composite sheet is reduced. Is improved.

In the adhesive composition and the film-like adhesive, the content of the epoxy-based thermosetting resin (b) (total content of the epoxy resin (b1) and the thermosetting agent (b2)) is the content of the polymer component (a). The content is preferably 50 to 1000 parts by mass, more preferably 100 to 900 parts by mass, and particularly preferably 150 to 870 parts by mass with respect to 100 parts by mass. When the content of the epoxy-based thermosetting resin (b) is in such a range, it becomes easier to separate the semiconductor chip provided with the film-like adhesive from the support sheet at the time of pickup.

In addition to the polymer component (a) and the epoxy-based thermosetting resin (b), the film-like adhesive contains other components that do not fall under these, if necessary, in order to improve its various physical properties. You may be doing it.
Other components contained in the film-like adhesive are preferable, for example, a curing accelerator (c), a filler (d), a coupling agent (e), a cross-linking agent (f), and an energy ray-curable resin. (G), a photopolymerization initiator (h), a general-purpose additive (i) and the like can be mentioned.

(Curing accelerator (c))
The curing accelerator (c) is a component for adjusting the curing rate of the adhesive composition.
Preferred curing accelerators (c) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole. , 2-Phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and other imidazoles (at least one hydrogen atom is other than a hydrogen atom) (Imidazole substituted with an organic group); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (phosphine in which at least one hydrogen atom is substituted with an organic group); tetraphenylphosphonium tetraphenylborate, triphenylphosphine. Examples thereof include tetraphenylboron salts such as tetraphenylborate.
Among the above, 2-phenyl-4,5-dihydroxymethylimidazole is preferable.

The curing accelerator (c) contained in the adhesive composition and the film-like adhesive may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected. ..

When the curing accelerator (c) is used, the content of the curing accelerator (c) in the adhesive composition and the film-shaped adhesive is 100 parts by mass with respect to the content of the epoxy-based thermosetting resin (b). , 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass. When the content of the curing accelerator (c) is at least the lower limit value, the effect of using the curing accelerator (c) is more remarkable. Further, when the content of the curing accelerator (c) is not more than the above upper limit value, for example, the highly polar curing accelerator (c) is an adherend in the film-like adhesive under high temperature and high humidity conditions. The effect of suppressing segregation by moving to the adhesive interface side with the film is enhanced, and the reliability of the package obtained by using the film-shaped adhesive composite sheet is further improved.

(Filler (d))
By containing the filler (d), the film-like adhesive makes it easy to adjust its thermal expansion coefficient, and by optimizing this thermal expansion coefficient for the object to which the film-like adhesive is attached, the film is formed. The reliability of the package obtained by using the adhesive composite sheet is further improved. Further, by containing the filler (d) in the film-shaped adhesive, it is possible to reduce the hygroscopicity of the film-shaped adhesive after curing and improve the heat dissipation.

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; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Goods; Single crystal fibers of these inorganic fillers; Glass fibers and the like.
Among these, the inorganic filler is preferably silica or alumina.

The filler (d) contained in the adhesive composition and the film-like adhesive may be of only one type, may be of two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When the filler (d) is used, the content of the filler (d) is the total mass of all the components outside the solvent constituting the adhesive composition (that is, the total mass of the film-like adhesive). It is preferably 5 to 80% by mass, more preferably 7 to 60% by mass. When the content of the filler (d) is in such a range, the above-mentioned coefficient of thermal expansion can be easily adjusted.

(Coupling agent (e))
By containing the coupling agent (e) in the film-like adhesive, the adhesiveness and adhesion to the adherend are improved. Further, when the film-like adhesive contains the coupling agent (e), the cured product has improved water resistance without impairing the 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 group of the polymer component (a), the epoxy thermosetting resin (b), etc., and is a silane coupling agent. Is more preferable.
Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-. (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino) Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include dimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfan, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, and epoxy group-containing oligomers.

The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be of only one type, of two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..
As one aspect, the coupling agent (e) is an epoxy group-containing oligomer-type silane coupling agent, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 2- (3,4-epoxy). It may be at least one selected from the group consisting of cyclohexyl) ethyltrimethoxysilane.

When the coupling agent (e) is used, the content of the coupling agent (e) in the adhesive composition and the film-like adhesive is the total of the polymer component (a) and the epoxy-based thermosetting resin (b). The content 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 with respect to 100 parts by mass.
When the content of the coupling agent (e) is at least the lower limit value, the dispersibility of the filler (d) in the resin is improved, the adhesiveness of the film-like adhesive to the adherend is improved, and the like. , The effect of using the coupling agent (e) is more remarkable. Further, when the content of the coupling agent (e) is not more than the upper limit value, the generation of outgas is further suppressed.

(Crosslinking agent (f))
As the polymer component (a), a polymer having a functional group such as a vinyl group capable of binding to another compound such as the acrylic resin described above, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group and an isocyanate group. When the components are used, the adhesive composition and the film-like adhesive may contain a cross-linking agent (f) for linking the functional group with another compound to cross-link. By cross-linking with the cross-linking agent (f), the initial adhesive force and the cohesive force of the film-like adhesive can be adjusted.

Examples of the cross-linking agent (f) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (a cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (a cross-linking agent having an aziridinyl group), and the like. Can be mentioned.

Examples of the organic polyvalent isocyanate compound include an aromatic polyhydric isocyanate compound, an aliphatic polyhydric isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”. (May be abbreviated); Trimerics such as the aromatic polyvalent isocyanate compound, isocyanurates and adducts; terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compounds and the like with a polyol compound. And so on. The "adduct" is a low content of the aromatic polyhydric isocyanate compound, the aliphatic polyhydric isocyanate compound or the alicyclic polyvalent isocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include a xylylene diisocyanate adduct of trimethylol propane as described later. Further, the "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at the terminal portion of the molecule.

More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4. , 4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Examples thereof include compounds in which one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or some hydroxylates of a polyol such as propane; lysine diisocyanate and the like.

Examples of the organic polyvalent imine compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylolpropane-tri-β-aziridinyl propionate, and tetramethylolmethane. Examples thereof include -tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylene melamine and the like.

When an organic multivalent isocyanate compound is used as the cross-linking agent (f), it is preferable to use a hydroxyl group-containing polymer as the polymer component (a). When the cross-linking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, the reaction between the cross-linking agent (f) and the polymer component (a) facilitates the cross-linking structure of the film-like adhesive. Can be introduced in.

The cross-linking agent (f) contained in the adhesive composition and the film-like adhesive may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

When the cross-linking agent (f) is used, the content of the cross-linking agent (f) in the adhesive composition is 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the polymer component (a). It is preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. When the content of the cross-linking agent (f) is at least the lower limit value, the effect of using the cross-linking agent (f) is more remarkable. Further, when the content of the cross-linking agent (f) is not more than the upper limit value, the excessive use of the cross-linking agent (f) is suppressed.

(Energy ray curable resin (g))
Since the film-like adhesive contains the energy ray curable resin (g), its characteristics can be changed by irradiation with energy rays.

The energy ray curable resin (g) has a property of being cured (polymerized) by irradiating with energy rays.
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 preferable.

Examples of the acrylate-based compound include trimethylolpropanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol monohydroxypenta (dipentaerythritol monohydroxypenta). Chain aliphatic skeleton-containing (meth) acrylates such as meta) acrylates, dipentaerythritol hexa (meth) acrylates, 1,4-butylene glycol di (meth) acrylates, and 1,6-hexanediol di (meth) acrylates; Cyclic aliphatic skeleton-containing (meth) acrylates such as cyclopentanyldi (meth) acrylates and tricyclodecanedimethylol diacrylates; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylates; oligoesters (meth) Examples thereof include acrylate; urethane (meth) acrylate oligomer; epoxy-modified (meth) acrylate; polyether (meth) acrylate other than the polyalkylene glycol (meth) acrylate; and itaconic acid oligomer.

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

The energy ray-curable resin (g) contained in the adhesive composition may be of only one type, may be two or more types, and when two or more types are used, the combination and ratio thereof can be arbitrarily selected.

In the adhesive composition, the content of the energy ray-curable resin (g) is preferably 1 to 95% by mass, preferably 1 to 95% by mass, based on the total mass of the components other than the solvent constituting the adhesive composition. It is more preferably 90% by mass, and particularly preferably 5 to 85% by mass.

(Photopolymerization Initiator (h))
When the adhesive composition contains the energy ray-curable resin (g), even if the photopolymerization initiator (h) is contained in order to efficiently proceed with the polymerization reaction of the energy ray-curable resin (g). good.

Examples of the photopolymerization initiator (h) in the adhesive composition include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate and benzoin dimethyl ketal. Compounds; Acetphenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6) -Trimethylbenzoyl) acylphosphine oxide compounds such as phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthium monosulfide; 1-hydroxycyclohexylphenylketone and the like. Α-Ketol compounds; azo compounds such as azobisisobutyronitrile; titanosen compounds such as titanosen; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethyl Thioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone can be mentioned.
Further, examples of the photopolymerization initiator (h) include a photosensitizer such as an amine.

The photopolymerization initiator (h) contained in the adhesive composition may be only one kind, may be two or more kinds, and when it is two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

In the adhesive composition, the content of the photopolymerization initiator (h) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the energy ray curable resin (g). It is more preferably 10 parts by mass, and particularly preferably 2 to 5 parts by mass.

(General-purpose additive (i))
The general-purpose additive (I) may be a known one and may be arbitrarily selected depending on the intended purpose, and is not particularly limited, but preferred ones are, for example, a plasticizer, an antistatic agent, an antioxidant, and a colorant (dye). , Pigments), gettering agents and the like.

The general-purpose additive (i) contained in the adhesive composition and the film-like adhesive may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected. ..
The contents of the adhesive composition and the film-like adhesive are not particularly limited and may be appropriately selected depending on the intended purpose.

(solvent)
The adhesive composition preferably further contains a solvent. The adhesive composition containing a solvent has good handleability.
The solvent is not particularly limited, but preferred ones are, for example, hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (also referred to as 2-methylpropane-1-ol), 1-butanol and the like. Alcohols; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond) and the like.
The solvent contained in the adhesive composition may be only one type, may be two or more types, and when two or more types are used, the combination and ratio thereof can be arbitrarily selected.

The solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the adhesive composition can be mixed more uniformly.

[Manufacturing method of adhesive composition]
The adhesive composition is obtained by blending each component for constituting the adhesive composition.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and diluted in advance, or any compounding component other than the solvent may be diluted in advance. You may use it by mixing the solvent with these compounding components without leaving it.

The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component is not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

In the film-like adhesive composite sheet of the present invention, the support sheet is made of a base material, and the base material is preferably provided with the film-like adhesive in direct contact with the base material. As described above, when the support sheet does not have the pressure-sensitive adhesive layer or the like and the film-like adhesive is directly provided on the base material, the components in the film-like adhesive are on the base material such as the pressure-sensitive adhesive layer. Interlayer movement of constituents is suppressed, such as migration to other layers, or conversely, components in such other layers to film-like adhesives, and during the manufacture of semiconductor devices. Occurrence of process abnormalities and deterioration of reliability of semiconductor packages are remarkably suppressed.
Normally, when a film-like adhesive composite sheet that does not have an adhesive layer is used, a double die is generated when the semiconductor chip is pulled away from the support sheet with the film-like adhesive attached. easy. However, if the film-shaped adhesive composite sheet of the present invention is used, the generation of double dies is suppressed even when the composite sheet does not have the pressure-sensitive adhesive layer.

<< Manufacturing method of film-shaped adhesive composite sheet >>
The film-shaped adhesive composite sheet of the present invention can be manufactured by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship. The method of forming each layer is as described above.
For example, when a pressure-sensitive adhesive layer is laminated on a base material when manufacturing a support sheet, the above-mentioned pressure-sensitive adhesive composition is applied onto the base material and dried as necessary to obtain a pressure-sensitive adhesive. Layers can be laminated.

On the other hand, for example, when a film-like adhesive is further laminated on a pressure-sensitive adhesive layer already laminated on a substrate, an adhesive composition is applied on the pressure-sensitive adhesive layer to obtain a film-like adhesive. It can be formed directly. As described above, when a continuous two-layer laminated structure is formed by using any of the compositions, the composition is further applied on the layer formed from the composition to form a new layer. Is possible to form. However, of these two layers, the layer to be laminated afterwards is formed in advance on another release film using the composition, and the side of the formed layer in contact with the release film is It is preferable to form a laminated structure of two continuous layers by laminating the exposed surface on the opposite side with the exposed surface of the remaining layers that have already been formed. At this time, it is preferable that the composition is applied to the peeled surface of the peeling film. The release film may be removed as necessary after the laminated structure is formed.

For example, a film-like adhesive composite sheet in which a pressure-sensitive adhesive layer is laminated on a base material and a film-like adhesive is laminated on the pressure-sensitive adhesive layer (that is, a support sheet is a laminate of a base material and a pressure-sensitive adhesive layer). In the case of producing a certain film-like adhesive composite sheet), the pressure-sensitive adhesive composition is applied onto the base material and dried as necessary to laminate the pressure-sensitive adhesive layer on the base material. Separately, the adhesive composition is applied onto the release film and dried as necessary to form a film-like adhesive on the release film, and the exposed surface of the film-like adhesive is used as a base material. A film-shaped adhesive composite sheet can be obtained by laminating the film-shaped adhesive on the pressure-sensitive adhesive layer by laminating it with the exposed surface of the pressure-sensitive adhesive layer already laminated.

When laminating the pressure-sensitive adhesive layer on the base material, the pressure-sensitive adhesive composition is coated on the release film instead of the method of coating the pressure-sensitive adhesive composition on the base material as described above. A pressure-sensitive adhesive layer is formed on the release film by drying as necessary, and the exposed surface of the pressure-sensitive adhesive layer is bonded to one surface of the base material to place the pressure-sensitive adhesive layer on the base material. It may be laminated on.
In either method, the release film may be removed at an arbitrary timing after the desired laminated structure is formed.

As described above, all the layers other than the base material constituting the film-shaped adhesive composite sheet can be laminated in advance by forming them on the release film and bonding them to the surface of the target layer, so that they can be laminated as needed. A film-like adhesive composite sheet may be produced by appropriately selecting a layer that employs such a process.

The film-shaped adhesive composite sheet is usually stored in a state where a release film is attached to the surface of the outermost layer (for example, a film-shaped adhesive) on the opposite side of the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as an adhesive composition, is applied onto the release film (preferably the release-treated surface thereof), and the film is dried as necessary. A layer constituting the outermost layer is formed on the release film, and the remaining layers are laminated on the exposed surface on the side opposite to the side in contact with the release film of this layer by any of the above methods. A film-like adhesive composite sheet can also be obtained by leaving the release film in a bonded state without removing it.

<< Manufacturing method of semiconductor device >>
The method for manufacturing a semiconductor device of the present invention is a method for manufacturing a semiconductor device using the film-shaped adhesive composite sheet, wherein the film-shaped adhesive composite sheet is divided into a plurality of pieces via a film-shaped adhesive. A film-like adhesive is provided for the step of sticking to the semiconductor chip (hereinafter, may be abbreviated as "sticking step") and the support sheet of the film-like adhesive composite sheet attached to the semiconductor chip. A step of applying a force to the film-like adhesive through the support sheet to cut the film-like adhesive by applying a force from the side opposite to the side where the adhesive is formed (hereinafter, may be abbreviated as "cutting step"). And a step of pulling the semiconductor chip and the cut film-like adhesive attached to the semiconductor chip away from the support sheet (hereinafter, may be abbreviated as "pulling step").

According to the manufacturing method, by using the film-shaped adhesive composite sheet, a process abnormality occurs in a semiconductor chip to which the film-shaped adhesive is attached by a simplified method at the time of manufacturing a semiconductor device. Can be suppressed and separated from the support sheet.

<Attachment process>
In the sticking step, the film-shaped adhesive composite sheet is stuck to a plurality of semiconductor chips that have been divided via the film-shaped adhesive. In this step, the film-like adhesive of one film-like adhesive composite sheet is attached to the back surface of a plurality of semiconductor chips.

The plurality of divided semiconductor chips form a groove from the surface of the semiconductor wafer opposite to the surface on which the film-shaped adhesive composite sheet is attached (the back surface of the semiconductor wafer), and the groove is reached until the groove is reached. It can be manufactured by grinding the back surface. As a method of forming the groove, for example, a method of forming a groove by cutting a semiconductor wafer with a blade (that is, blade dicing) and a method of forming a groove by cutting a semiconductor wafer by laser irradiation (that is, that is). Laser dicing), a method of forming a groove by cutting a semiconductor wafer by spraying water containing an abrasive (that is, water dicing) and the like can be mentioned.

Further, after the plurality of divided semiconductor chips are irradiated with laser light in the infrared region so as to be focused on the focal point set inside the semiconductor wafer, a modified layer is formed inside the semiconductor wafer. By grinding the back surface of the semiconductor wafer and further applying a force to the semiconductor wafer after grinding the back surface, or by applying a force during grinding to the semiconductor wafer being ground on the back surface. It can also be manufactured by dividing the semiconductor wafer at the formation site of the modified layer.

<Cutting process>
In the cutting step, after the sticking step, a force is applied to the support sheet in the film-shaped adhesive composite sheet stuck to the semiconductor chip from the side opposite to the side on which the film-shaped adhesive is provided. , A force is applied to the film-like adhesive through the support sheet to cut the film-like adhesive. Hereinafter, the manufacturing method of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing an embodiment of the manufacturing method of the present invention, from cutting a film-like adhesive to pulling a semiconductor chip away from a support sheet. In FIG. 1, only the configuration related to the film-shaped adhesive composite sheet is shown in cross section.

As shown in FIG. 1A, the film-like adhesive 12 of the film-like adhesive composite sheet 1 is attached to the back surface 9b of the plurality of semiconductor chips 9 by the attachment step. Then, in this step, on the surface (also referred to as the back surface) 11b of the support sheet 11 of the film-like adhesive composite sheet 1 opposite to the surface (also referred to as the front surface) 11a on which the film-like adhesive 12 is provided. Among the semiconductor device manufacturing devices (not shown in the overall view), the push-up portion 81 that pushes up the semiconductor chip is in contact with the device.

When the support sheet 11 is a sheet made of a base material, the film-like adhesive composite sheet 1 has a base material and a film-like adhesive 12 laminated on the side of the film-like adhesive 12 in contact with the base material. The front surface on the opposite side is attached to the back surface 9b of the semiconductor chip 9.
When the support sheet 11 is a sheet in which the base material and the pressure-sensitive adhesive layer are laminated, the film-like adhesive composite sheet 1 has the base material, the pressure-sensitive adhesive layer and the film-like adhesive 12 laminated in this order, and is a film. The surface of the adhesive 12 on the side opposite to the side in contact with the adhesive layer is attached to the back surface 9b of the semiconductor chip 9.

In this step, as shown in FIG. 1B, a force is applied to the support sheet 11 of the film-like adhesive composite sheet 1 from the back surface 11b thereof to bond the film-like adhesive through the support sheet 11. Apply force to agent 12. Here, the protrusion (pin) 811 protrudes from the push-up portion 81, and the tip portion of the protrusion 811 pushes up the support sheet 11 from the back surface 11b thereof, so that the protrusion 811 is opposed to the film-like adhesive 12 via the support sheet 11. An example of applying a force in the protruding direction of is shown. At this time, the pushing conditions such as the protruding amount (pushing amount), the protruding speed (pushing speed), and the holding time of the protruding state (lifting waiting time) of the protrusion 811 can be appropriately adjusted.
Here, the case where the number of protrusions 811 pushing up the support sheet 11 is one is shown, but the number may be two or more, and the number of protrusions 811 may be appropriately selected.

According to the film-shaped adhesive composite sheet 1, when a force is applied to the film-shaped adhesive 12 in this way, the shearing force generated by pushing up the protrusion 811 suppresses the occurrence of process abnormalities while suppressing the occurrence of process abnormalities. The adhesive 12 can be cut. More specifically, the film-like adhesive 12 can be cut at room temperature at a target portion, that is, a portion surrounding only the semiconductor chip 9 that is to be separated from the support sheet 11. Then, for example, a step mainly for cutting the film-shaped adhesive 12, such as a step of irradiating the film-shaped adhesive 12 with a laser to cut the film-shaped adhesive 12, a step of cutting by expanding the film-shaped adhesive 12, and the like, are separately performed. Can be cut without provision.

<Pulling process>
In the separating step, after the cutting step, as shown in FIG. 1 (c), the semiconductor chip 9 and the cut film-like adhesive 12 attached to the semiconductor chip 9 are separated (picked up) from the support sheet 11. .. This step is usually carried out continuously immediately after the cutting step. Here, an example is shown in which the film-like adhesive 12 after cutting attached to the semiconductor chip 9 is peeled off from the support sheet 11 by pulling up the semiconductor chip 9 by the pulling-up portion 82 of the semiconductor device manufacturing apparatus. .. The method of pulling up the semiconductor chip 9 in this way may be a known method, and examples thereof include a method of adsorbing and pulling up the surface of the semiconductor chip 9 with a vacuum collet.

According to the film-shaped adhesive composite sheet 1, when the semiconductor chip 9 is pulled up in this way, the film-shaped adhesive 12 can be peeled off from the support sheet 11 while suppressing the occurrence of process abnormalities. More specifically, the portion of the film-shaped adhesive 12 corresponding to the target semiconductor chip 9 is peeled off from the support sheet 11, and the portion of the film-shaped adhesive 12 corresponding to the unintended semiconductor chip 9 is formed. The phenomenon of peeling from the support sheet 11 is suppressed. Then, since the film-shaped adhesive 12 is cut at a predetermined position, the pulled-up semiconductor chip 9 is pulled away from the support sheet 11 together with the film-shaped adhesive 12.

In the manufacturing method of the present invention, the semiconductor device separated (picked up) together with the film-like adhesive is used, and thereafter, the semiconductor device is manufactured by the same method as the conventional method. For example, the semiconductor chip is die-bonded to the circuit surface of the substrate with a film-like adhesive, and if necessary, at least one semiconductor chip is further laminated on the semiconductor chip to perform wire bonding, and then the whole is resin. By sealing with, it becomes a semiconductor package. Then, the target semiconductor device may be manufactured by using this semiconductor package.

The method for manufacturing the semiconductor device of the present invention is not limited to the above-mentioned method described with reference to FIG. It may be an added one.
For example, as a method of applying a force to the film-like adhesive 12 through the support sheet 11, a method of applying a force to the film-like adhesive 12 by pushing up the support sheet 11 by a protrusion 811 has been described so far. As another method, for example, a method of applying a force to the film-like adhesive 12 by pushing up the support sheet 11 with a slider instead of the protrusion 811 can be mentioned.

FIG. 2 is a cross-sectional view for schematically explaining another embodiment of applying a force to the above-mentioned film-like adhesive to cut the film-like adhesive. In FIG. 2, the same components as those shown in FIG. 1 are designated by the same reference numerals as those in FIG. 1, and detailed description thereof will be omitted. This also applies to the figures after FIG.
What is shown here is an alternative to the method described with reference to FIG. 1 (b) as a method for cutting the film-like adhesive.

Also in the case of applying the present embodiment, first, the pasting step is performed by the same method as described with reference to FIG. 1 (a).
Next, by applying a force to the support sheet 11 of the film-shaped adhesive composite sheet 1 from the back surface 11b, a force is applied to the film-shaped adhesive 12 through the support sheet 11. However, in the present embodiment, instead of the protrusion 811 as shown in FIG. 1 (b) in the push-up portion 81, the slider 812 is moved as shown in FIGS. 2 (a) and 2 (b). The support sheet 11 is pushed up from its back surface 11b.

In the present embodiment, as shown in FIG. 2A, the front surface 812a of the slider 812 protruding from the push-up portion 81 is in contact with the back surface 11b of the support sheet 11. At this time, the front surface 812a of the slider 812 is not parallel to the back surface 11b of the support sheet 11 before the cutting step as shown in FIG. 1 (a). Therefore, by applying a force to the support sheet 11 from the back surface 11b in the direction orthogonal to the front surface 812a of the slider 812, that is, in the diagonal direction instead of the vertical direction, the push-up height of the film-like adhesive 12 is different. Occurs. However, the force applied to the film-like adhesive 12 through the support sheet 11 is the same as in the case of FIG. 1 (b). As a result, among the regions where the film-like adhesive 12 has a high push-up height, the shearing force generated by the push-up is generated in the region where the semiconductor chip 9 is not attached (the first region 121 in FIG. 2A). Therefore, the film-like adhesive 12 can be cut while suppressing the occurrence of process abnormalities.

At the time of pushing up by the slider 812, the pushing up conditions such as the protrusion amount (pushing amount), the inclination angle (pushing speed), and the moving speed (lifting waiting time) of the slider 812 can be appropriately adjusted.

In the present embodiment, then, as shown in FIG. 2B, the slider 812 is moved in a direction parallel to the back surface 11b of the support sheet 11 which is not pushed up. As a result, the push-up portion of the support sheet 11 moves. Then, after the movement of the push-up portion, the push-up is performed in the region where the semiconductor chip 9 is not attached (second region 122 in FIG. 2B) in the region where the push-up height of the film-like adhesive 12 is high. The film-like adhesive 12 can be cut while suppressing the occurrence of process abnormalities due to the shearing force generated in association with the above.

Due to the shearing force generated by the movement of the slider 812, the film-like adhesive 12 is cut while suppressing the occurrence of process abnormalities, as in the case described with reference to FIG.
Hereinafter, the pulling step can be performed by the same method as described with reference to FIG. 1 (a).

However, in general, the pin-pushing method as described with reference to FIG. 1 has a higher cutting effect on the film-like adhesive than the slider-pushing method as described with reference to FIG. Therefore, it is preferable to select which method to use in consideration of the strength-related characteristics such as the breaking elongation B of the film-like adhesive.

As described above, according to the method for manufacturing a semiconductor device of the present invention, the film-like adhesive can be cut at a target portion in the cutting step, so that the semiconductor chip is not cut due to the film-like adhesive not being cut. Defects in pulling (lifting) are suppressed.
Further, according to the method for manufacturing a semiconductor device of the present invention, in the peeling step, the target portion of the film-like adhesive is peeled from the support sheet, so that the occurrence of peeling (lifting) failure of the semiconductor chip is suppressed. .. Further, since the non-target portion of the film-like adhesive is suppressed from peeling from the support sheet, not only the target semiconductor chip but also the semiconductor chip adjacent to the target semiconductor chip is simultaneously pulled away from the support sheet together with the film-like adhesive. The generation of so-called double dies is suppressed.
As described above, according to the present invention, it is possible to manufacture a semiconductor device by suppressing the occurrence of process abnormalities by a simplified method.

When the film-shaped adhesive composite sheet of the present invention is not used, it may not be possible to suppress the occurrence of process abnormalities as shown below during the manufacture of the semiconductor device.

FIG. 3 is a cross-sectional view schematically showing one aspect of the film-shaped adhesive composite sheet and the semiconductor chip in the manufacturing process of the semiconductor device when the conventional film-shaped adhesive composite sheet is used.
When the film-shaped adhesive composite sheet 7 shown in FIG. 3 is used, as shown in FIG. 3A, even if a force is applied to the film-shaped adhesive 72, the film-shaped adhesive 72 is not cut, and further. When the semiconductor chip 9 is pulled up, the film-like adhesive 72 is peeled off from the semiconductor chip 9 and remains laminated on the support sheet 71. As a result, as shown in FIG. 3B, a defective lifting of the semiconductor chip 9 occurs.
Such a process abnormality is caused by, for example, in the film-shaped adhesive composite sheet 7, the values of the breaking elongation B and the breaking strength C are large, and the adhesion is compared with the values of the breaking elongation B and the breaking strength C. It tends to occur when the value of the force A is so small that it is not desirable and the relationship of the above equation (1) is not satisfied.

FIG. 4 is a cross-sectional view schematically showing another aspect of the film-shaped adhesive composite sheet and the semiconductor chip in the manufacturing process of the semiconductor device when the conventional film-shaped adhesive composite sheet is used.
When the film-like adhesive composite sheet 7 shown in FIG. 4 is used, as shown in FIG. 4A, only a notch is formed in a part of the film-like adhesive 72, and the film-like adhesive 72 is cut. Further, when the semiconductor chip 9 is pulled up, the film-like adhesive 72 is peeled off from the semiconductor chip 9 and remains laminated on the support sheet 71. As a result, as shown in FIG. 4B, a defective lifting of the semiconductor chip 9 occurs.
In such a process abnormality, for example, in the film-shaped adhesive composite sheet 7, the values of the breaking elongation B and the breaking strength C are large, and the adhesion when compared with the values of the breaking elongation B and the breaking strength C. It tends to occur when the value of the force A is so small that it is not desirable and the relationship of the above equation (1) is not satisfied.

The process abnormality described with reference to FIGS. 3 to 4 is an example, and other process abnormalities may occur in some cases.
On the other hand, when the film-shaped adhesive composite sheet of the present invention is used, the occurrence of such process abnormalities is suppressed, and as a result, a semiconductor device can be manufactured inexpensively by a method simplified as compared with the conventional method. can.

As one aspect of the film-like adhesive composite sheet according to one embodiment of the present invention,
A film-like adhesive composite sheet,
The film-like adhesive composite sheet is placed on a support sheet having a base material.
A curable film-like adhesive with a thickness of 1 to 50 μm, preferably 3 to 25 μm, more preferably 5 to 15 μm is provided;
The adhesive strength of the film-shaped adhesive before curing to the semiconductor wafer is set to adhesive strength A (N / 24 mm), and the film-shaped adhesive before curing is laminated so that the total thickness is 200 μm. When the breaking elongation is defined as the breaking elongation B (%) and the breaking strength of the laminated body is defined as the breaking strength C (MPa).
The adhesive strength A is 0.3 to 15N / 24mm, preferably 0.3 to 11N / 24mm, more preferably 0.4 to 7N / 24mm, still more preferably 0.45N / 24mm or more and less than 10N / 24mm. Particularly preferably, it is 0.45N / 24mm or more and 5.8N / 24mm or less;
The elongation at break B is 1200% or less, preferably 30 to 1200%, more preferably 40 to 1100%, even more preferably 45 to 1050%, or 30 to 500%, 40 to 500%, 45 to 500. % Or 50-440%;
The breaking strength C is 0.4 to 17 MPa, preferably 0.5 to 15 MPa, more preferably 0.6 to 13 MPa, still more preferably 0.8 to 11 MPa, particularly preferably 2.5 to 11 MPa; and A. The value of / (B × C) is 0.0005 or more and 0.0170 or less, preferably 0.0006 or more and 0.0140 or less, more preferably 0.00067 or more and 0.0115 or less, and further preferably 0.0008 or more and 0. Less than 0.0125, 0.0008 or more and 0.0105 or less,
Examples thereof include a film-like adhesive composite sheet.

As another aspect of the film-like adhesive composite sheet according to one embodiment of the present invention,
The film-like adhesive composite sheet.
Further, the film-like adhesive is
It is formed from an adhesive composition containing a polymer component (a), an epoxy-based thermosetting resin (b), a filler (d), and a coupling agent (e);
The polymer component (a) is composed of an acrylic resin having a weight average molecular weight (Mw) of 1000 to 2000000, preferably butyl acrylate, methyl acrylate, glycidyl methacrylate, and 2-hydroxyethyl acrylate. The selected monomer is a copolymerized resin;
The epoxy-based thermosetting resin (b) is composed of an epoxy resin (b1) and a thermosetting agent (b2).
The epoxy resin (b1) is preferably at least one selected from the group consisting of a bisphenol A type epoxy resin, a phenylene skeleton type epoxy resin, and a dicyclopentadiene type epoxy resin;
The filler (d) is silica or alumina;
The coupling agent (e) is an epoxy group-containing oligomer-type silane coupling agent, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltri. At least one selected from the group consisting of methoxysilanes;
The content of the acrylic resin of the polymer component (a) is 5 to 40% by mass, preferably 7 to 25% by mass, or 9 to 28% by mass with respect to the total mass of the film-shaped adhesive. May be;
The content of the epoxy-based thermosetting resin (b) is 50 to 1000 parts by mass, preferably 100 to 900 parts by mass, and more preferably 150 parts by mass with respect to 100 parts by mass of the polymer component (a). ~ 870 parts by weight; or may be 47-81% by weight or 47-80% by weight;
The content of the filler (d) is 5 to 80% by mass, preferably 7 to 60% by mass, or 8 to 12% by mass or 9 to 12% by mass, based on the total mass of the film-like adhesive. May be%;
The content of the coupling agent (e) is preferably 0.03 to 20 parts by mass with respect to 100 parts by mass of the total content of the polymer component (a) and the epoxy-based thermosetting resin (b). Is 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, or may be 0.28 to 1% by mass.
Examples thereof include a film-like adhesive composite sheet.

Furthermore, the film-like adhesive composite sheet is
The base material is a base material in which a layer made of low-density polyethylene, a layer containing polypropylene, a styrene / ethylenebutylene / styrene block copolymer, and a layer made of low-density polyethylene are laminated in this order. May be.

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

The components used in the production of the adhesive composition are shown below.
Polymer component (a) -1: butyl acrylate (hereinafter abbreviated as "BA") (55 parts by mass), methyl acrylate (hereinafter abbreviated as "MA") (10 parts by mass), methacrylic acid. Acrylic resin (weight) obtained by copolymerizing glycidyl (hereinafter abbreviated as "GMA") (20 parts by mass) and -2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (15 parts by mass). Average molecular weight 800,000, glass transition temperature −28 ° C.).
(A) -2: An acrylic resin obtained by copolymerizing MA (85 parts by mass) and HEA (15 parts by mass) (weight average molecular weight 370000, glass transition temperature 6 ° C.).
(A) -3: An acrylic resin obtained by copolymerizing MA (95 parts by mass) and HEA (5 parts by mass) (weight average molecular weight 760000, glass transition temperature 9 ° C.).
(A) -4: Thermoplastic resin, polyester ("Byron 220" manufactured by Toyobo Co., Ltd., weight average molecular weight 35000, glass transition temperature 53 ° C.))
Epoxy resin (b1) -1: Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "JER828", epoxy equivalent 184 to 194 g / eq)
(B1) -2: Liquid bisphenol A type epoxy resin ("JER834" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 250 g / eq, weight average molecular weight 470)
(B1) -3: Polyfunctional aromatic type (triphenylene type) epoxy resin ("EPPN-502H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 167 g / eq, softening point 54 ° C., weight average molecular weight 1200)
(B1) -4: Cresol novolac type epoxy resin to which an acryloyl group is added ("CNA147" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 518 g / eq, number average molecular weight 2100, unsaturated group content is equal to that of epoxy group)
(B1) -5: Dicyclopentadiene type epoxy resin ("ADEKA Resin EP-4088L" manufactured by ADEKA, epoxy equivalent 165 g / eq)
Thermosetting agent (b2) -1: Novolac type phenol resin ("BRG-556" manufactured by Showa Denko KK, softening point 80 ° C., weight average molecular weight 950)
(B2) -2: Biphenyl-type phenol resin ("MEH-7851-SS" manufactured by Meiwakasei Co., Ltd., softening point 67 ° C.)
(B2) -3: Aralkyl type phenol resin ("Millex XLC-4L" manufactured by Mitsui Chemicals, Inc., softening point 63 ° C.)
-Curing accelerator (c) -1: 2-phenyl-4,5-dihydroxymethylimidazole ("Curesol 2PHZ" manufactured by Shikoku Chemicals Corporation)
-Filler (d) -1: Spherical silica ("SC2050MA" manufactured by Admatex Co., Ltd.)
(D) -2: Spherical silica ("SC2050" manufactured by Admatex)
(D) -3: Spherical silica ("YA050C-MJE" manufactured by Admatex)
-Coupling agent (e) -1: Silane coupling agent, epoxy group-containing oligomer type (Mitsubishi Chemical "MKC silicate MSEP-2", epoxy equivalent 222 g / eq)
(E) -2: Silane coupling agent, epoxy group-containing oligomer type ("X-41-1056" manufactured by Shinetsu Silicone Co., Ltd., epoxy equivalent 280 g / eq)
(E) -3: Silane coupling agent, 3-glycidyloxypropyltrimethoxysilane (“KBM-403” manufactured by Shinetsu Silicone Co., Ltd.)
(E) -4: Silane coupling agent, 3-glycidyloxypropyltriethoxysilane (“KBE-403” manufactured by Shinetsu Silicone Co., Ltd.)
(E) -5: Silane coupling agent, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (“KBM-303” manufactured by Shinetsu Silicone Co., Ltd.)
(E) -6: Silane coupling agent, 3-glycidyloxypropylmethyldiethoxysilane (“KBE-402” manufactured by Shinetsu Silicone Co., Ltd.)
-Crosslinking agent (f) -1: Torishenisocyanate-based crosslinking agent ("Coronate L" manufactured by Tosoh Corporation)
-Energy ray curable resin Energy ray curable resin (g) -1: Tricyclodecanedimethyloldiacrylate ("KAYARAD R-684" manufactured by Nippon Kayaku Co., Ltd., ultraviolet curable resin, molecular weight 304)
Photopolymerization Initiator Photopolymerization Initiator (h) -1: 1-Hydroxycyclohexylphenyl ketone (“IRGACURE 184” manufactured by BASF)
-Other ingredients (z) -1: Silicone oil ("XF42-334" manufactured by Momentive Performance Materials Japan)

The base material used for manufacturing the film-shaped adhesive composite sheet is shown below.
Substrate (1): A layer made of low-density polyethylene (“Novatec LC520” manufactured by Nippon Polyethylene Co., Ltd., density 0.923 g / cm ³ , MFR 3.6 g / 10 minutes, thickness 8 μm) and a layer containing polypropylene (homopolypropylene). Resin ("Prime Polypro F-300SP" manufactured by Prime Polymer Co., Ltd., density 0.90 g / cm ³ , MFR 3.0 g / 10 minutes) and styrene / polyethylene butylene / styrene block copolymer ("Dynaron 8601P" manufactured by JSR Co., Ltd., density A layer consisting of a mixture of 0.89 g / cm ³ , MFR 3.5 g / 10 min) (thickness 60 μm) and a layer made of low density polyethylene (same as above except that the thickness is 12 μm instead of 8 μm). And is a base material laminated in this order. The above MFR (melt flow rate) is measured at 190 ° C. for low-density polyethylene, 230 ° C. for homopolypropylene resin, and styrene / ethylenebutylene / styrene block copolymer in accordance with JISK7210: 1999. Is a value measured at 230 ° C. and a load of 21.18N.
Base material (2): A base material having a two-layer structure in which a layer made of a polyethylene-methacrylic acid copolymer and a layer made of polyethylene are laminated (“HUSL1301” manufactured by Achilles Corporation).

<Manufacturing of film-like adhesive composite sheet>
[Example 1]
(Manufacturing of adhesive composition)
Polymer component (a) -1, polymer component (a) -4, epoxy resin (b1) -1, epoxy resin (b1) -3, thermosetting agent (b2) -1, curing accelerator (c)- 1. Filling material (d) -1, coupling agent (e) -1, energy ray curable resin (g) -1, and photopolymerization initiator (h) -1 are contained in these contents (parts by mass). Was dissolved or dispersed in methyl ethyl ketone so as to have the values shown in Table 1, and stirred at 23 ° C. to obtain an adhesive composition having a solid content concentration of 50% by mass. In addition, the description of "-" in the column of the contained component in Table 1 means that the adhesive composition does not contain the component.

(Manufacturing of film-shaped adhesive composite sheet)
The adhesive composition obtained above was applied to the peeled surface of the peeled film (“SP-PET3811” manufactured by Lintec Corporation, thickness 38 μm) from which one side of the polyethylene terephthalate film was peeled, and 3 at 100 ° C. By drying for a minute, a film-like adhesive having a thickness of 7 μm was formed. Next, a layer made of low-density polyethylene having a thickness of 8 μm of the base material (1) was bonded to the exposed surface of the film-shaped adhesive to obtain a film-shaped adhesive composite sheet.

[Examples 2 to 5, Comparative Examples 1 to 2]
A film-shaped adhesive composite sheet was produced by the same method as in Example 1 except that the components contained in the base material or the adhesive composition were as shown in Table 1.
When the base material (2) was used, the polyethylene layer was attached to the exposed surface of the film-like adhesive.

<Evaluation of film-like adhesive composite sheet>
The following items were evaluated for each of the film-like adhesive composite sheets of Examples and Comparative Examples obtained above.

(Measurement of adhesive force A)
The film-shaped adhesive composite sheet is cut into a size of 24 mm × 300 mm, the film-shaped adhesive is heated to 60 ° C., and cellophane tape (“Cellotape (registered trademark) No.” manufactured by Nichiban Co., Ltd. .405 ”, width 24 mm) was attached. Next, the substrate was peeled off from the film-like adhesive, and the exposed film-like adhesive was attached to the dry-polished surface of a 6-inch silicon wafer (thickness 350 μm) while being heated to 60 ° C. to form a test piece. , Cellophane tape, film-like adhesive and silicon wafer were laminated in this order to obtain a laminate.
The obtained laminate was immediately left for 30 minutes in an environment of 23 ° C. and a relative humidity of 50% (under the standard environment specified in JIS Z0237 2009), and then a film-like adhesive and a cellophane tape were released from the silicon wafer. The laminated laminated sheet is peeled off at a peeling speed of 150 mm / min so that the surfaces of the film-like adhesive and the silicon wafer that were in contact with each other form an angle of 180 °, that is, so-called 180 ° peeling is performed. The peeling force was measured, and the measured value was taken as the adhesive force A (N / 24 mm). The results are shown in Table 1.

(Measurement of elongation at break B)
Using a laminator, two film-shaped adhesives (thickness 20 μm) are heated to 60 ° C. and bonded together, and the same film-shaped adhesive is bonded in the same manner until the total thickness is 200 μm. A laminated body in which a certain film-like adhesive was laminated was produced.
The resulting laminate was then heated for 30 seconds using a hot plate heated to 80 ° C. Next, using a super cutter (“PH1-600” manufactured by Ogino Seiki Seisakusho), this heated laminate was cut within 10 seconds to prepare a test piece having a width of 15 mm, a length of 100 mm, and a thickness of 200 μm. .. If the cutting time exceeds 10 seconds, the cutting is stopped once, the laminated body being cut is heated again using a hot plate heated to 80 ° C., and then the cutting is performed within 10 seconds for the test. Pieces were made. In this way, the reason why the laminated body is cut after heating is to prevent a defect portion that causes breakage from occurring at the end portion of the test piece.

Then, the elongation at break was measured for the obtained test piece in accordance with JIS K7161-1994. More specifically, it is as follows.
That is, a universal testing machine (“Autograph AG-IS 500N” manufactured by Shimadzu Corporation) was used, and the test piece was fixed at two places by the fixing gripping device. At this time, the distance between the tips of the fixed gripping instruments (the length of the exposed portion of the test piece, the distance between the fixed portions) was set to 75 mm.
Then, the tensile speed was set to 200 mm / min, the test piece was pulled between the fixed portions, the breaking elongation of the test piece was obtained, and the breaking elongation was B (%). The results are shown in Table 1.

(Measurement of breaking strength C)
At the time of the above-mentioned breaking elongation B measurement, the tensile stress when the test piece was broken (broken), that is, the tensile breaking stress was measured, and the measured value was defined as the breaking strength C (MPa). The results are shown in Table 1.

(Calculation of A / (B × C) value)
The value of A / (B × C) was calculated from the measured values of the adhesive force A, the breaking elongation B and the breaking strength C obtained above. The results are shown in Table 1.

(Evaluation of pickup suitability by pushing up with a pin)
An 8-inch silicon wafer was fragmented into chips of 2 mm × 2 mm and a thickness of 50 μm. Then, using a laminator, the film-like adhesive of the film-like adhesive composite sheet was heated to 60 ° C., and the heated film-like adhesive was bonded to the dry-polished surface of the chip. By the above operation, a test sheet in which one film-like adhesive composite sheet was attached to a large number of silicon chips was obtained.
Next, for this test sheet, a pickup device (“BESTEM-D02” manufactured by Canon Machinery Co., Ltd.) was used, and the push-up amount was 150 μm, the push-up speed was 20 mm / min, and the lift waiting time was 1 sec. , Picked up 54 times. When the pickup was successful 40 times or more, it was determined that the pickup suitability was good (X), and in other cases, it was determined that the pickup suitability was poor (Y). The results are shown in Table 1.

(Evaluation of pickup suitability by pushing up with a slider)
Except for the fact that the slider kit was attached to the pickup device used in the above-mentioned evaluation of pickup suitability, and the pickup device had the same configuration as that shown in FIG. 2, the pickup was performed by the slider push-up method. The pickup suitability was evaluated by the same method as in the case of the pin push-up method. At this time, the pickup was performed under the conditions of a stroke distance of 1.5 mm, a stroke speed of 90 mm / sec, and a waiting time of 1 sec. The results are shown in Table 1.

As is clear from the above results, the film-like adhesive composite sheets of Examples 1 to 5 have A / (B × C) values in the range of 0.0008 or more, and satisfy the relationship of the above formula (1). Was there. In the silicon chip to which the film-like adhesive of these sheets is attached, the one-pin push-up method suppresses the occurrence of process abnormalities without separately providing a process mainly for cutting the film-like adhesive. While doing so, I was able to cut the film-like adhesive. Furthermore, the silicon chip to which the film-like adhesive after cutting was attached could be separated from the support sheet while suppressing the occurrence of process abnormalities. As described above, the film-shaped adhesive composite sheets of Examples 1 to 5 showed good pickup suitability in the one-pin push-up method.

Further, when the film-shaped adhesive composite sheet of Examples 1 to 2, 4 to 5 in which the breaking elongation B of the film-shaped adhesive is in the range of 440% or less is used, even with the slider push-up method, 1 pin is used. As in the case of the push-up method, it showed good pickup suitability.

On the other hand, the film-shaped adhesive composite sheets of Comparative Examples 1 and 2 had an A / (B × C) value in the range of 0.0004 or less and did not satisfy the relationship of the above formula (1). .. In the silicon chip to which the film-like adhesive of these sheets is attached, in both the 1-pin push-up method and the slider push-up method, from the cutting of the film-like adhesive to the support sheet of the silicon chip with the film-like adhesive. During the period from when the film was separated from the film, the number of occurrences of process abnormalities was large, and the pick-up suitability was poor.

The present invention is extremely useful industrially because it can be used in the manufacture of semiconductor devices.

1 ... film-like adhesive composite sheet, 11 ... support sheet, 11a ... front surface of support sheet, 11b ... back surface of support sheet, 12 ... film-like adhesive, 9 ... semiconductor Chip, 9b ... Back side of semiconductor chip

Claims (4)

A film-like adhesive composite sheet,
In the film-like adhesive composite sheet, a curable film-like adhesive having a thickness of 1 to 50 μm is provided on a support sheet having a base material;
The adhesive strength of the film-shaped adhesive before curing to the semiconductor wafer is set to adhesive strength A (N / 24 mm), and the film-shaped adhesive before curing is laminated so that the total thickness is 200 μm. When the breaking elongation is defined as the breaking elongation B (%) and the breaking strength of the laminated body is defined as the breaking strength C (MPa), the following formula (1) is used.
A / (B × C) ≧ 0.0005 ・ ・ ・ ・ (1)
Satisfy the relationship,
The breaking elongation B is 30 to 1200%, and the breaking elongation B is 30 to 1200%.
The film-shaped adhesive composite sheet is intended to be used in a method for manufacturing a semiconductor device.
The method for manufacturing the semiconductor device includes a step of attaching the film-shaped adhesive composite sheet to a plurality of divided semiconductor chips via the film-shaped adhesive.
By applying a force to the support sheet in the film-like adhesive composite sheet attached to the semiconductor chip from the side opposite to the side on which the film-like adhesive is provided, the film-like adhesive sheet is passed through the support sheet. The step of applying force to the adhesive to cut the film-like adhesive, and
A step of separating the semiconductor chip and the film-like adhesive after cutting attached to the semiconductor chip from the support sheet, and
Including, film-like adhesive composite sheet. The film-like adhesive composite sheet according to claim 1, wherein the elongation at break B is 500% or less. The film-shaped adhesive composite sheet according to claim 1 or 2, wherein the support sheet is made of the base material, and the film-shaped adhesive is provided in direct contact with the base material. It is a manufacturing method of semiconductor devices.
A step of attaching the film-shaped adhesive composite sheet according to any one of claims 1 to 3 to a plurality of semiconductor chips that have been divided via the film-shaped adhesive.
By applying a force to the support sheet in the film-like adhesive composite sheet attached to the semiconductor chip from the side opposite to the side on which the film-like adhesive is provided, the film-like adhesive sheet is passed through the support sheet. The step of applying force to the adhesive to cut the film-like adhesive, and
A step of separating the semiconductor chip and the film-like adhesive after cutting attached to the semiconductor chip from the support sheet, and
A method for manufacturing a semiconductor device, including.

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